Functionalized Ethylene/Alpha-Olefin Interpolymer Compositions

ABSTRACT

The invention relates to functionalized interpolymers derived from base olefin interpolymers, which are prepared by polymerizing one or more monomers or mixtures of monomers, such as ethylene and one or more comonomers, to form an interpolymer products having unique physical properties. The functionalized olefin interpolymers contain two or more differing regions or segments (blocks), resulting in unique processing and physical properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 11/376,863 filed on Mar. 15, 2006 which claims priority to PCTApplication No. PCT/US2005/008917 (Dow 63558D), filed on Mar. 17, 2005,which in turn claims priority to U.S. Provisional Application No.60/553,906, filed Mar. 17, 2004. The application further claims priorityto U.S. Provisional Application Ser. No. 60/718,184 filed Sep. 16, 2005(Dow 64397) and 60/718,000 filed Sep. 16, 2005. For purposes of UnitedStates patent practice, the content of each foregoing application isincorporated by reference herein in its entirety.

FIELD OF THE INVENTION

This invention relates to functionalized ethylene/α-olefin interpolymercompositions.

BACKGROUND AND SUMMARY OF THE INVENTION

Base interpolymers have been prepared by polymerizing one or moremonomers or mixtures of monomers such as ethylene and one or morecomonomers, to form interpolymer products having unique physicalproperties such as two or more differing regions or segments (blocks),which provide unique physical properties. Such olefin interpolymers aredescribed in PCT Application No. 2005/08917, filed Mar. 17, 2005, whichis incorporated herein, in its entirety, by reference.

Despite the discovery of the multi-block interpolymers as discussedabove, there remains a need to develop olefin interpolymers, which arewell suited as compatibilizing agents for compatibilizing incompatiblepolymer blends; and thus, which can be used to develop new polymeralloys. There is also a need to develop olefin interpolymers for use inthe development of products with targeted differentiated properties. Forexample, there is a need to develop olefin interpolymers for compoundingor polymer modification formulations, each used to improve theprocessibilty and performance of the resulting polymer composition,and/or to improve the properties of the final polymer product and/or toimprove the cost-efficiency of producing the final product. There is aneed for improved polymers for the modification of engineeringthermoplastics and polyolefins, resulting in new resins withimprovements in one or more of the following properties: viscosity, heatresistance, impact resistance, toughness, flexibility, tensile strength,compression set, stress relaxation, creep resistance, tear strength,blocking resistance, solidification temperature, abrasion resistance,retractive force, oil retention, pigment retention and filler capacity.It would be useful if such olefin interpolymers could be blended intothermoset systems, such as epoxies, unsaturated polyesters, and thelike, prior to curing, or during curing, to improve the performance ofthe cured thermoset in properties, such as, for example, impactresistance, toughness and flexibility.

In addition, there is a need to develop olefin interpolymers for use incoatings, adhesive and tie layer applications, where such polyolefinsprovide strong adhesion to polar and/or nonpolar substrates, improvepaintability an/or printability, provide good flexibility, and providestructural and chemical stability over a broad service temperaturerange. Substrates may include, but are not limited to, otherpolyolefins, polyamides, polyesters, polycarbonate, other engineeringthermoplastics, polyvinylidene chloride, polyvinyl chloride, polyvinylalcohol, cellulose, glass, and metals. At least some of theaforementioned needs and other are met by the following invention.

The invention provides functionalized derivatives of the segmented ormulti-block interpolymers, as described herein, and provides forcompositions comprising the same. The functionalized interpolymers ofthis invention often exhibit lower viscosities for better melt flows andlower operating temperatures in various processing applications. Theinvention also relates to methods of using these functionalizedinterpolymers in applications requiring unique combinations ofprocessing elements and unique physical properties in the final product.In still another aspect, the invention relates to the articles preparedfrom these functionalized interpolymers. These functionalizedmulti-block interpolymers and polymeric blends, containing the same, maybe employed in the preparation of solid articles, such as moldings,films, sheets, and foamed objects. These articles may be prepared bymolding, extruding, or other processes. The functionalized interpolymersare useful in adhesives, tie layers, laminates, polymeric blends, andother end uses. The resulting products may be used in the manufacture ofcomponents for automobiles, such as profiles, bumpers and trim parts, ormay be used in the manufacture of packaging materials, electric cableinsulation, coatings and other applications.

In one aspect, the invention provides a composition, comprising at leastone functionalized olefin interpolymer, and wherein the functionalizedolefin interpolymer is formed from an olefin interpolymer having atleast one melting point, T_(m), in degrees Celsius, and a density, d*,in grams/cubic centimeter, and wherein the numerical values of thevariables correspond to the relationship:

T _(m)>−2002.9+4538.5(d*)−2422.2(d*)²,and

wherein the interpolymer has a M_(w)/M_(n) from 1.7 to 3.5.

In another aspect, the invention provides a composition, comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymerhaving the following:

a) a Mw/Mn from 1.7 to 3.5,

b) a delta quantity (tallest DSC peak minus tallest CRYSTAF peak)greater than the quantity, y*, defined by the equation:y*>−0.1299(ΔH)+62.81, and

c) a heat of fusion up to 130 J/g, and

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C., andwherein ΔH is the numerical value of the heat of fusion in J/g.

In another aspect, the invention provides a composition comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymerthat has a delta quantity (tallest DSC peak (measured from the baseline)minus tallest CRYSTAF peak) greater than 48° C., and a heat of fusiongreater than, or equal to, 130 J/g, and wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.

In another aspect, the invention provides a composition comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymerthat has a mole percent of at least one commoner in a TREF fractionbetween 40° C. and 130° C., as determined according to the followingformula:

y≧{−0.2013(TREF Elution Temp.)+21.07},

wherein “y” is the mole percent comonomer(s) in the TREF fractionbetween 40° C. and 130° C.

In another aspect, the invention provides a composition, comprising atleast one functionalized multi-block interpolymer, and wherein thefunctionalized multi-block interpolymer is prepared from a multi-blockinterpolymer that comprises, in polymerized form, ethylene and one ormore copolymerizable comonomers, and wherein said multi-blockinterpolymer comprises two or more segments, or blocks, differing incomonomer content, crystallinity, density, melting point or glasstransition temperature, and wherein the multi-block interpolymer isfunctionalized with at least one compound, selected from the groupconsisting of unsaturated compounds containing at least one heteroatom.

In yet another aspect, the invention provides a process for preparing afunctionalized multi-block interpolymer of the invention, said processcomprising, reacting the multi-block interpolymer with the at least onecompound, and at least one initiator, and wherein the at least oneinitiator generates 0.01 millimoles to 10 millimoles radicals per 100grams of the multi-block interpolymer, and wherein the at least onecompound is present in an amount from 0.05 to 10 parts per hundred gramof the multi-block interpolymer.

In another aspect, the invention provides a composition, comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymercomprising ethylene and one or more copolymerizable comonomers inpolymerized form, and wherein said olefin interpolymer comprisesmultiple blocks or segments of two or more polymerized monomer units,said blocks or segments differing in chemical or physical properties(blocked interpolymer), and wherein the olefin interpolymer has amolecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, and wherein said fraction has amolar comonomer content higher than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, and whereinsaid comparable random ethylene interpolymer comprises the samecomonomer(s), and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer, and wherein the olefin interpolymer is functionalized withat least one unsaturated compound containing at least one heteroatom.

In another aspect, the invention provides a composition, comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymercomprising ethylene and one or more copolymerizable comonomers inpolymerized form, and wherein the olefin interpolymer comprises multipleblocks or segments of two or more polymerized monomer units, said blocksor segments differing in chemical or physical properties (blockedinterpolymer), and wherein the olefin interpolymer has a peak (but notjust a molecular fraction) which elutes between 40° C. and 130° C. (butwithout collecting and/or isolating individual fractions), and whereinsaid peak, has an average comonomer content, determine by infra-redspectroscopy when expanded using a full width/half maximum (FWHM) areacalculation, higher than that of a comparable random ethyleneinterpolymer peak at the same elution temperature and expanded using afull width/half maximum (FWHM) area calculation, and wherein saidcomparable random ethylene interpolymer comprises the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the blocked interpolymer,and wherein the olefin interpolymer is functionalized with at least oneunsaturated compound containing at least one heteroatom.

In another aspect, the invention provides a composition, comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymercomprising ethylene and one or more copolymerizable comonomers inpolymerized form, and wherein the olefin interpolymer comprises multipleblocks or segments of two or more polymerized monomer units, said blocksor segments differing in chemical or physical properties (blockedinterpolymer), and wherein the olefin interpolymer has a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, and wherein those fractions that have a comonomercontent of at least about 6 mole percent, have a melting point greaterthan about 100° C., and wherein those fractions having a comonomercontent from about 3 mole percent to about 6 mole percent, have a DSCmelting point of about 110° C. or higher, and wherein the olefininterpolymer is functionalized with at least one unsaturated compoundcontaining at least one heteroatom.

In another aspect, the invention provides a composition, comprising atleast one functionalized olefin interpolymer, and wherein thefunctionalized olefin interpolymer is formed from an olefin interpolymercomprising ethylene and one or more copolymerizable comonomers inpolymerized form, and wherein the olefin interpolymer comprises multipleblocks or segments of two or more polymerized monomer units, said blocksor segments differing in chemical or physical properties (blockedinterpolymer), and wherein the olefin interpolymer has a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, and wherein every fraction that has an ATREFelution temperature greater than, or equal to, about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation: Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58, and wherein every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation: Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97, and wherein the olefin interpolymer is functionalizedwith at least one unsaturated compound containing at least oneheteroatom.

The invention also provides for crosslinked derivatives of theaforementioned functionalized olefin interpolymers. The invention alsoprovides for additional embodiments of the above compositions,functionalized interpolymers, and processes, all as described herein,and for combinations of two or more of these embodiments. The inventionfurther provides for articles, each comprising at least one componentthat comprises, or is formed from, a composition as described herein,and provides for processes for preparing the same.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer examples 10-19. The “X” symbols represent polymer examplesA*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from inventive interpolymers (represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare various Dow AFFINITY® polymers). The squares represent inventiveethylene/butene copolymers; and the circles represent inventiveethylene/octene copolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and comparative polymers E and F (represented by the “X” symbols). Thediamonds represent traditional random ethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for comparativeF (curve 2). The squares represent Example F*; and the trianglesrepresent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene-copolymer (curve 3) and for two ethylene/1-octeneblock copolymers of the invention made with differing quantities ofchain shuttling agent (curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some inventivepolymers (represented by the diamonds), as compared to some knownpolymers. The triangles represent various Dow VERSIFY® polymers; thecircles represent various random ethylene/styrene copolymers; and thesquares represent various Dow AFFINITY® polymers.

FIG. 8 is an FTIR spectrum of Multi-block R22 grafted with 0.77 wt %maleic anhydride. The boxed portion of the spectrum indicates thecarbonyl region of the spectrum (2000-1500 cm¹).

FIG. 9 represents an overlay of the carbonyl regions of the FTIR spectraof, from top to bottom, Multi-block R22 grafted with 0.77% MAH;Multi-block R21 grafted with 0.76% MAH; EO870 grafted with 0.58% MAH;and unfunctionalized EO870.

FIG. 10 is a FTIR spectrum of Multi-block R22, grafted with 3.50 wt %vinyltriethoxysilane (VTES). The boxed portion of the spectrum indicatesthe Si—O—C region of the spectrum (1400-900 cm⁻¹).

FIG. 11 is an overlay of the Si—O—C absorption regions of the FTIRspectra of, from top to bottom, Multi-block R22 grafted with 3.50% VTES;Multi-block R21 grafted with 3.53% VTES; EO870 grafted with 3.59% VTES;and unfunctionalized EO870.

FIG. 12 is a graph showing the comparison of thermal properties ofAFFINITY® GA1950, Multi-block 500, si-AFFINITY® GA 1950, andsi-Multi-block 500.

FIG. 13 is a graph showing the comparison of mechanical properties ofAFFINITY® GA1950, Multi-block 500, si-AFFINITY® GA 1950, andsi-Multi-block 500.

FIG. 14 is a graph showing the comparison of storage modulus G′ ofAFFINITY® GA1950, Multi-block 500, si-AFFINITY® GA 1950, andsi-Multi-block 500.

FIG. 15 is a graph showing the comparison of tan delta of AFFINITY®GA1950, Multi-block 500, si-AFFINITY® GA 1950, and si-Multi-block 500.

FIG. 16 is a graph showing the melt strength modification of amulti-block interpolymer functionalized with various amounts ofperoxide.

FIG. 17 is a graph showing the melt strength modification of amulti-block interpolymer functionalized with various amounts of (bis)sulfonyl azide.

FIG. 18 is a graph showing the melt shear rheology (viscosity versusfrequency) of a multi-block interpolymer functionalized with variousamounts of peroxide.

FIG. 19 is a graph showing the melt shear rheology (viscosity versusfrequency) a multi-block interpolymer functionalized with variousamounts of (bis) sulfonyl azide.

FIG. 20 is a graph showing the 70° C. compression set of a multi-blockinterpolymer functionalized with various amounts of (bis) sulfonyl azideand the 70° C. compression set of a multi-block interpolymerfunctionalized with various amounts of peroxide.

DETAILED DESCRIPTION OF THE INVENTION General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The ethylene/α-olefin interpolymers comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. That is, theethylene/α-olefin interpolymers are block interpolymers, preferablymulti-block interpolymers or copolymers. The terms “interpolymer” andcopolymer” are used interchangeably herein. In some embodiments, themulti-block copolymer can be represented by the following formula:

(AB)_(n)

where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.

AAA-AA-BBB-BB

In still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which ethylene is present in an amount greater than about 95weight percent, and preferably greater than about 98 weight percentbased on the weight of the polymer. In other words, the comonomercontent (content of monomers other than ethylene) in the hard segmentsis less than about 5 weight percent, and preferably less than about 2weight percent based on the weight of the polymer. In some embodiments,the hard segments comprises all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 50 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in aconcurrently filed U.S. patent application Ser. No. ______ (insert whenknown), Attorney Docket No. 385063-999558, entitled “Ethylene/α-OlefinBlock Interpolymers”, filed on Mar. 15, 2006, in the name of Colin L. P.Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global TechnologiesInc., the disclose of which is incorporated by reference herein in itsentirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the amount or type of comonomer incorporated therein,the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess making of the copolymers. More specifically, when produced in acontinuous process, the polymers desirably possess PDI from 1.7 to 2.9,preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and mostpreferably from 1.8 to 2.1. When produced in a batch or semi-batchprocess, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to1.8.

“Impact-modifying amount of ethylene/α-olefin multi-block interpolymer”is a quantity of ethylene/α-olefin multi-block interpolymer added to agiven polymer composition such that the composition's notched Izodimpact strength at room temperature or below is maintained or increasedas compared to said given composition's notched Izod impact strength atthe same temperature without the added ethylene/α-olefin multi-blockinterpolymer.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R═R^(L)+k*(R^(U)—R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

Ethylene/α-Olefin Interpolymers

The ethylene/α-olefin interpolymers used in embodiments of the invention(also referred to as “inventive interpolymer” or “inventive polymer”)comprise ethylene and one or more copolymerizable α-olefin comonomers inpolymerized form, characterized by multiple blocks or segments of two ormore polymerized monomer units differing in chemical or physicalproperties (block interpolymer), preferably a multi-block copolymer. Theethylene/α-olefin interpolymers are characterized by one or more of theaspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:

T _(m)>−2002.9+4538.5(d)−2422.2(d)²,and preferably

T _(m)≧−6288.1+13141(d)−6720.3(d)²,and more preferably

T _(m)≧858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:

ΔT>−0.1299(ΔH)+62.81,and preferably

ΔT≧−0.1299(ΔH)+64.38,and more preferably

ΔT≧−0.1299(ΔH)+65.95,

for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:

Re>1481−1629(d);and preferably

Re≧1491−1629(d);and more preferably

Re≧1501−1629(d);and even more preferably

Re≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength≧11 MPa, morepreferably a tensile strength≧13 MPa and/or an elongation at break of atleast 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G′(25° C.)/G′(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, whereT_(i) and T₂ are points determined, to the left and right of the ATREFpeak, by dividing the peak height by two, and then drawing a linehorizontal to the base line, that intersects the left and right portionsof the ATREF curve. A calibration curve for comonomer content is madeusing random ethylene/α-olefin copolymers, plotting comonomer contentfrom NMR versus FWHM area ratio of the TREF peak. For this infra-redmethod, the calibration curve is generated for the same comonomer typeof interest. The comonomer content of TREF peak of the inventive polymercan be determined by referencing this calibration curve using its FWHMmethyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers has highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013) T+20.07 (solid line). The line for the equation (−0.2013)T+21.07 is depicted by a dotted line. Also depicted are the comonomercontents for fractions of several block ethylene/1-octene interpolymersof the invention (multi-block copolymers). All of the block interpolymerfractions have significantly higher 1-octene content than either line atequivalent elution temperatures. This result is characteristic of theinventive interpolymer and is believed to be due to the presence ofdifferentiated blocks within the polymer chains, having both crystallineand amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F to be discussed below.The peak eluting from 40 to 130° C., preferably from 60° C. to 95° C.for both polymers is fractionated into three parts, each part elutingover a temperature range of less than 10° C. Actual data for Example 5is represented by triangles. The skilled artisan can appreciate that anappropriate calibration curve may be constructed for interpolymerscontaining different comonomers and a line used as a comparison fittedto the TREF values obtained from comparative interpolymers of the samemonomers, preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. Inventive interpolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same TREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(−0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013) T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:

Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion(J/gm)<(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion(J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.

ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170., both ofwhich are incorporated by reference herein in their entirety.

In other embodiments, the inventive ethylene/α-olefin interpolymer ischaracterized by an average block index, ABI, which is greater than zeroand up to about 1.0 and a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. The average block index, ABI, is the weightaverage of the block index (“BI”) for each of the polymer fractionsobtained in preparative TREF from 20° C. and 110° C., with an incrementof 5° C.:

ABI=Σ(w _(i)BI_(i))

where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction, BI is defined by one of the two followingequations (both of which give the same BI value):

${BI} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\mspace{14mu} {or}\mspace{14mu} {BI}} = {- \frac{{{Ln}\; P_{X}} - {{Ln}\; P_{XO}}}{{{Ln}\; P_{A}} - {{Ln}\; P_{AB}}}}}$

where T_(X) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(X) is the ethylene molefraction for the ith fraction, which can be measured by NMR or IR asdescribed above. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372° K, P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB). T_(AB) canbe calculated from the following equation:

Ln P _(AB) =α/T _(AB)+β

where α and β are two constants which can be determined by calibrationusing a number of known random ethylene copolymers. It should be notedthat α and β may vary from instrument to instrument. Moreover, one wouldneed to create their own calibration curve with the polymer compositionof interest and also in a similar molecular weight range as thefractions. There is a slight molecular weight effect. If the calibrationcurve is obtained from similar molecular weight ranges, such effectwould be essentially negligible. In some embodiments, random ethylenecopolymers satisfy the following relationship:

Ln P=−237.83/T _(ATREF)+0.639

T_(XO) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(X). T_(XO) can becalculated from Ln P_(X)=α/T_(XO)+β. Conversely, P_(XO) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(X), which can be calculated from LnP_(XO)=α/T_(X)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.3 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. In some embodiments, the polymer fraction has a block index greaterthan about 0.6 and up to about 1.0, greater than about 0.7 and up toabout 1.0, greater than about 0.8 and up to about 1.0, or greater thanabout 0.9 and up to about 1.0. In other embodiments, the polymerfraction has a block index greater than about 0.1 and up to about 1.0,greater than about 0.2 and up to about 1.0, greater than about 0.3 andup to about 1.0, greater than about 0.4 and up to about 1.0, or greaterthan about 0.4 and up to about 1.0. In still other embodiments, thepolymer fraction has a block index greater than about 0.1 and up toabout 0.5, greater than about 0.2 and up to about 0.5, greater thanabout 0.3 and up to about 0.5, or greater than about 0.4 and up to about0.5. In yet other embodiments, the polymer fraction has a block indexgreater than about 0.2 and up to about 0.9, greater than about 0.3 andup to about 0.8, greater than about 0.4 and up to about 0.7, or greaterthan about 0.5 and up to about 0.6.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog (G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/566,2938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconiumdibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents. The shuttling agents employed include diethylzinc,di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That, is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or it may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is malicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400−600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431(M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\% \mspace{14mu} {Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$

where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\% \mspace{14mu} {Stress}\mspace{14mu} {Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$

where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat #Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec². The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents. The shuttling agents employed include diethylzinc(DEZ, SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3),triethylaluminum (TEA, SA4), trioctylaluminum (SA5), triethylgallium(SA6), i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7),i-butylaluminum bis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA17), n-octylaluminumbis(dimethyl(t-butyl)siloxide(SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4 Comparative A-C General High Throughput ParallelPolymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density.

TABLE 1 Cat. (A1) Cat (B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol)(μmol) agent (μmol) Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 —0.1363 300502 3.32 — B* — 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.060.1 0.176 0.8 — 0.2038 45526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0) 0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.1214.4 3 0.06 0.1 0.192 — TEA (8.0)  0.208 22675 1.71 4.6 4 0.06 0.1 0.192— TEA (80.0) 0.1879 3338 1.54 9.4 ¹C⁶ or higher chain content per 1000carbons ²Bimodal molecular weight distribution

It may be seen the polymers produced according to the invention have arelatively narrow polydispersity (Mw/Mn) and larger block-copolymercontent (trimer, tetramer, or larger) than polymers prepared in theabsence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for comparative A shows a 90.0° C. melting point (Tm) witha heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows thetallest peak at 48.5° C. with a peak area of 29.4 percent. Both of thesevalues are consistent with a resin that is low in density. Thedifference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for comparative B shows a 129.8° C. melting point (Tm)with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for comparative C shows a 125.3° C. melting point (Tm)with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19 Comparatives D-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3.

TABLE 2 Process details for preparation of exemplary polymers Cat Cat A1Cat B2 DEZ DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow ConcFlow Conc. Flow [C₂H₄]/ Rate⁵ Conv Solids Ex. kg/hr kg/hr sccm¹ ° C. ppmkg/hr ppm kg/hr % kg/hr ppm kg/hr [DEZ]⁴ kg/hr %⁶ % Eff.⁷ D* 1.63 12.729.90 120 142.2 0.14 — — 0.19 0.32 820 0.17 536 1.81 88.8 11.2 95.2 E* ″9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3 126.8 F* ″11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3 257.7 5 ″ ″— ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1 118.3 6 ″ ″4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1 172.7 7 ″ ″21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.2 10.6 244.1 8 ″ ″36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778 1.62 90.0 10.8 261.1 9 ″ ″ 78.43 ″″ ″ ″ ″ ″ 0.04 ″ ″ 4596 1.63 90.2 10.8 267.9 10 ″ ″ 0.00 123 71.1 0.1230.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1 131.1 11 ″ ″ ″ 12071.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.56 11.1 100.6 12 ″ ″ ″121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.02 11.3 137.0 13 ″ ″ ″122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.64 11.2 161.9 14 ″ ″ ″120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.42 9.3 114.1 15 2.45 ″″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.33 11.3 121.3 16 ″ ″ ″122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.11 11.2 159.7 17 ″ ″ ″121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.08 11.0 155.6 18 0.69 ″ ″121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.93 8.8 90.2 19 0.32 ″ ″122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.74 8.4 106.0*Comparative, not an example of the invention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl ³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor ⁵polymer production rate⁶percent ethylene conversion in reactor ⁷efficiency, kg polymer/g Mwhere g M = g Hf + g Zr

TABLE 3 Properties of exemplary polymers Heat of Tm- CRYSTAF Density MwMn Fusion T_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20 5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60 6 0.8785 1.1 7.5 6.5 109600 533002.1 55 115 94 44 71 63 7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69 121103 49 72 29 8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 80 43 139 0.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 16 10 0.8784 1.27.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.1 59.2 6.566,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4 101,50055,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,100 63,600 2.142 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9 123 121 10673 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 91 32 82 10 160.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 17 0.8757 1.711.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.1 24.9 6.172,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.0 76,80039,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of comparative D shows a peak with a 37.3°C. melting point (Tm) with a heat of fusion of 31.6 J/g. Thecorresponding CRYSTAF curve shows no peak equal to and above 30° C. Bothof these values are consistent with a resin that is low in density. Thedelta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of comparative E shows a peak with a124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.3° C. with apeak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of comparative F shows a peak with a124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 77.6° C. with apeak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is a substantially linear ethylene/1-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene/1-octenecopolymer (AFFINITY®EG8100, available from The Dow Chemical Company),Comparative I is a substantially linear ethylene/1-octene copolymer(AFFINITY®PL1840, available from The Dow Chemical Company), ComparativeJ is a hydrogenated styrene/butadiene/styrene triblock copolymer(KRATON™ G1652, available from KRATON Polymers), Comparative K is athermoplastic vulcanizate (TPV, a polyolefin blend containing dispersedtherein a crosslinked elastomer). Results are presented in Table 4.

TABLE 4 High Temperature Mechanical Properties 300% Pellet Strain TMA-1mm Blocking Recovery Compression penetration Strength G′(25° C.)/ (80°C.) Set (70° C.) Ex. (° C.) lb/ft² (kPa) G′(100° C.) (percent) (percent)D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed 100  5 1040 (0) 6 81 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4 Failed 41  997 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 79 13 95 — 6 8471 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0 (0) 4 82 47 18125 — 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed 100 H* 70 213(10.2) 29 Failed 100 I* 111 — 11 — — J* 107 — 5 Failed 100 K* 152 — 3 —40

In Table 4, Comparative F (which is a physical blend of the two polymersresulting from simultaneous polymerizations using catalyst A1 and B1)has a 1 mm penetration temperature of about 70° C., while Examples 5-9have a 1 mm penetration temperature of 100° C. or greater. Further,examples 10-19 all have a 1 mm penetration temperature of greater than85° C., with most having 1 mm TMA temperature of greater than 90° C. oreven greater than 100° C. This shows that the novel polymers have betterdimensional stability at higher temperatures compared to a physicalblend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperatureof about 107° C., but it has very poor (high temperature 70° C.)compression set of about 100 percent and it also failed to recover(sample broke) during a high temperature (80° C.) 300 percent strainrecovery. Thus the exemplified polymers have a unique combination ofproperties unavailable even in some commercially available, highperformance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative F) has a storage modulus ratio of 9 and arandom ethylene/octene copolymer (Comparative G) of similar density hasa storage modulus ratio an order of magnitude greater (89). It isdesirable that the storage modulus ratio of a polymer be as close to 1as possible. Such polymers will be relatively unaffected by temperature,and fabricated articles made from such polymers can be usefully employedover a broad temperature range. This feature of low storage modulusratio and temperature independence is particularly useful in elastomerapplications such as in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers of the inventionpossess improved pellet blocking strength. In particular, Example 5 hasa pellet blocking strength of 0 MPa, meaning it is free flowing underthe conditions tested, compared to Comparatives F and G which showconsiderable blocking. Blocking strength is important since bulkshipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparatives F, G, H and J all have a 70° C. compression setof 100 percent (the maximum possible value, indicating no recovery).Good high temperature compression set (low numerical values) isespecially needed for applications such as gaskets, window profiles,o-rings, and the like.

TABLE 5 Ambient Temperature Mechanical Properties Elon- Elon- Abra-Tensile 100% Retractive gation gation sion: Notched Strain 300% StrainStress at Stress Flex Tensile Tensile at Tensile at Volume Tear RecoveryRecovery 150% Compression Relaxation Modulus Modulus Strength Break¹Strength Break Loss Strength 21° C. 21° C. Strain Set 21° C. at 50% Ex.(MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ) (percent) (percent) (kPa)(Percent) Strain² D* 12 5 — — 10 1074 — — 91 83 760 — — E* 895 589 — 311029 — — — — — — — F* 57 46 — — 12 824 93 339 78 65 400 42 — 5 30 24 14951 16 1116 48 — 87 74 790 14 33 6 33 29 — — 14 938 — — — 75 861 13 — 744 37 15 846 14 854 39 — 82 73 810 20 — 8 41 35 13 785 14 810 45 461 8274 760 22 — 9 43 38 — — 12 823 — — — — — 25 — 10 23 23 — — 14 902 — — 8675 860 12 — 11 30 26 — — 16 1090 — 976 89 66 510 14 30 12 20 17 12 96113 931 — 1247 91 75 700 17 — 13 16 14 — — 13 814 — 691 91 — — 21 — 14212 160 — — 29 857 — — — — — — — 15 18 14 12 1127 10 1573 — 2074 89 83770 14 — 16 23 20 — — 12 968 — — 88 83 1040 13 — 17 20 18 — — 13 1252 —1274 13 83 920 4 — 18 323 239 — — 30 808 — — — — — — — 19 706 483 — — 36871 — — — — — — — G* 15 15 — — 17 1000 — 746 86 53 110 27 50 H* 16 15 —— 15 829 — 569 87 60 380 23 — I* 210 147 — — 29 697 — — — — — — — J* — —— — 32 609 — — 93 96 1900 25 — K* — — — — — — — — — — — 30 — ¹Tested at51 cm/minute ²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F, G and H have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative G. Lower stress relaxation means that the polymer retainsits force better in applications such as diapers and other garmentswhere retention of elastic properties over long time periods at bodytemperatures is desired.

Optical Testing

TABLE 6 Polymer Optical Properties Ex. Internal Haze (percent) Clarity(percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56  5 13 72 60  6 3369 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 67 11 13 69 67 12 875 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 6122 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of examples 5, 7 and Comparative Eare conducted. In the experiments, the polymer sample is weighed into aglass fritted extraction thimble and fitted into a Kumagawa typeextractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flaskis then fitted to the extractor. The ether is heated while beingstirred. Time is noted when the ether begins to condense into thethimble, and the extraction is allowed to proceed under nitrogen for 24hours. At this time, heating is stopped and the solution is allowed tocool. Any ether remaining in the extractor is returned to the flask. Theether in the flask is evaporated under vacuum at ambient temperature,and the resulting solids are purged dry with nitrogen. Any residue istransferred to a weighed bottle using successive washes of hexane. Thecombined hexane washes are then evaporated with another nitrogen purge,and the residue dried under vacuum overnight at 40° C. Any remainingether in the extractor is purged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7.

TABLE 7 ether ether C₈ hexane hexane C₈ residue wt. soluble soluble molesoluble soluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g)(percent) percent¹ percent¹ Comp. 1.097 0.063 5.69 12.2 0.245 22.35 13.66.5 F* Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.0171.59 13.3 0.012 1.10 11.7 9.9 ¹Determined by ¹³C NMR

Additional Polymer Examples 19A-J Continuous Solution Polymerization,Catalyst A1/B2+DEZ For Examples 19A-I

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from Exxon Mobil, Inc.), ethylene, 1-octene, and hydrogen(where used) are combined and fed to a 27 gallon reactor. The feeds tothe reactor are measured by mass-flow controllers. The temperature ofthe feed stream is controlled by use of a glycol cooled heat exchangerbefore entering the reactor. The catalyst component solutions aremetered using pumps and mass flow meters. The reactor is run liquid-fullat approximately 550 psig pressure. Upon exiting the reactor, water andadditive are injected in the polymer solution. The water hydrolyzes thecatalysts, and terminates the polymerization reactions. The post reactorsolution is then heated in preparation for a two-stage devolatization.The solvent and unreacted monomers are removed during the devolatizationprocess. The polymer melt is pumped to a die for underwater pelletcutting.

For Example 19J

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil, Inc.),ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, and hydrogen (whereused) are supplied to a 3.8 L reactor equipped with a jacket fortemperature control and an internal thermocouple. The solvent feed tothe reactor is measured by a mass-flow controller. A variable speeddiaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer.

Process details and results are contained in Table 8. Selected polymerproperties are provided in Tables 9A-C.

In Table 9B, inventive examples 19F and 19G show low immediate set ofaround 65-70% strain after 500% elongation.

TABLE 8 Polymerization Conditions Cat Cat Cat A1² Cat A1 B2³ B2 DEZ DEZC₂H₄ C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Flow Ex. lb/hr lb/hrlb/hr sccm¹ ° C. ppm lb/hr ppm lb/hr wt % lb/hr 19A 55.29 32.03 323.03101 120 600 0.25 200 0.42 3.0 0.70 19B 53.95 28.96 325.3 577 120 6000.25 200 0.55 3.0 0.24 19C 55.53 30.97 324.37 550 120 600 0.216 2000.609 3.0 0.69 19D 54.83 30.58 326.33 60 120 600 0.22 200 0.63 3.0 1.3919E 54.95 31.73 326.75 251 120 600 0.21 200 0.61 3.0 1.04 19F 50.4334.80 330.33 124 120 600 0.20 200 0.60 3.0 0.74 19G 50.25 33.08 325.61188 120 600 0.19 200 0.59 3.0 0.54 19H 50.15 34.87 318.17 58 120 6000.21 200 0.66 3.0 0.70 19I 55.02 34.02 323.59 53 120 600 0.44 200 0.743.0 1.72 19J 7.46 9.04 50.6 47 120 150 0.22 76.7 0.36 0.5 0.19 [Zn]⁴Cocat 1 Cocat 1 Cocat 2 Cocat 2 in Poly Conc. Flow Conc. Flow polymerRate⁵ Conv⁶ Polymer Ex. ppm lb/hr ppm lb/hr ppm lb/hr wt % wt % Eff.⁷19A 4500 0.65 525 0.33 248 83.94 88.0 17.28 297 19B 4500 0.63 525 0.1190 80.72 88.1 17.2 295 19C 4500 0.61 525 0.33 246 84.13 88.9 17.16 29319D 4500 0.66 525 0.66 491 82.56 88.1 17.07 280 19E 4500 0.64 525 0.49368 84.11 88.4 17.43 288 19F 4500 0.52 525 0.35 257 85.31 87.5 17.09 31919G 4500 0.51 525 0.16 194 83.72 87.5 17.34 333 19H 4500 0.52 525 0.70259 83.21 88.0 17.46 312 19I 4500 0.70 525 1.65 600 86.63 88.0 17.6 27519J — — — — — — — — — ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl ⁴ppm in final product calculated by mass balance⁵polymer production rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 9A Polymer Physical Properties Heat of Tm − CRYSTAF Density Mw MnFusion Tm Tc TCRYSTAF TCRYSTAF Peak Area Ex. (g/cc) I2 I10 I10/I2(g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.) (wt %) 19A0.8781 0.9 6.4 6.9 123700 61000 2.0 56 119 97 46 73 40 19B 0.8749 0.97.3 7.8 133000 44300 3.0 52 122 100 30 92 76 19C 0.8753 5.6 38.5 6.981700 37300 2.2 46 122 100 30 92 8 19D 0.8770 4.7 31.5 6.7 80700 397002.0 52 119 97 48 72 5 19E 0.8750 4.9 33.5 6.8 81800 41700 2.0 49 121 9736 84 12 19F 0.8652 1.1 7.5 6.8 124900 60700 2.1 27 119 88 30 89 89 19G0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19H 0.8654 1.07.0 7.1 131600 66900 2.0 26 118 88 — — — 19I 0.8774 11.2 75.2 6.7 6640033700 2.0 49 119 99 40 79 13 19J 0.8995 5.6 39.4 7.0 75500 29900 2.5 101122 106 — — —

TABLE 9B Polymer Physical Properties of Compression Molded FilmImmediate Immediate Immediate Set after Set after Set after RecoveryRecovery Recovery Density Melt Index 100% Strain 300% Strain 500% Strainafter 100% after 300% after 500% Example (g/cm³) (g/10 min) (%) (%) (%)(%) (%) (%) 19A 0.878 0.9 15 63 131 85 79 74 19B 0.877 0.88 14 49 97 8684 81 19F 0.865 1 — — 70 — 87 86 19G 0.865 0.9 — — 66 — — 87 19H 0.8650.92 — 39 — — 87 —

TABLE 9C Average Block Index For exemplary polymers¹ Example Zn/C₂ ²Average BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the calculation of the block indicesfor various polymers is disclosed in U.S. Patent Application Serial No.    (insert when known), entitled “Ethylene/α-Olefin BlockInterpolymers”, filed on Mar. 15, 2006, in the name of Colin L. P. Shan,Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc.,the disclose of which is incorporated by reference herein in itsentirety. ²Zn/C₂ * 1000 = (Zn feed flow * Zn concentration/1000000/Mw ofZn)/(Total Ethylene feed flow * (1 − fractional ethylene conversionrate)/Mw of Ethylene) * 1000. Please note that “Zn” in “Zn/C₂ * 1000”refers to the amount of zinc in diethyl zinc (“DEZ”) used in thepolymerization process, and “C2” refers to the amount of ethylene usedin the polymerization process.

Functionalized Ethylene/α-Olefin Interpolymers

The multi-block olefin interpolymers disclosed above may be modified by,for example, grafting, hydrogenation, nitrene insertion reactions, orother functionalization reactions such as those known to those skilledin the art. Preferred functionalizations are grafting reactions using afree radical mechanism.

A variety of radically graftable species may be attached to the polymer,either individually, or as relatively short grafts. These speciesinclude unsaturated molecules, each containing at least one heteroatom.These species include, but are not limited to, maleic anhydride, dibutylmaleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate,N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride,bromomaleic anhydride, chloromaleic anhydride, nadic anhydride,methylnadic anhydride, alkenylsuccinic anhydride, maleic acid, fumaricacid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid,and the respective esters, imides, salts, and Diels-Alder adducts ofthese compounds. These species also include silane compounds.

Radically graftable species of the silane class of materials may beattached to the polymer, either individually, or as relatively shortgrafts. These species include, but are not limited to,vinylalkoxysilanes, vinyltrimethoxysilane, vinyltriethoxysilane,vinyltriacetoxysilane, vinyltrichlorosilane, and the like. Generally,materials of this class include, but are not limited to, hydrolyzablegroups, such as alkoxy, acyloxy, or halide groups, attached to silicon.Materials of this class also include non-hydrolyzable groups, such asalkyl and siloxy groups, attached to silicon.

Other radically graftable species may be attached to the polymer,individually, or as short-to-longer grafts. These species include, butare not limited to, methacrylic acid; acrylic acid; Diels-Alder adductsof acrylic acid; methacrylates including methyl, ethyl, butyl, isobutyl,ethylhexyl, lauryl, stearyl, hydroxyethyl, and dimethylaminoethyl;acrylates including methyl, ethyl, butyl, isobutyl, ethylhexyl, lauryl,stearyl, and hydroxyethyl; glycidyl methacrylate; trialkoxysilanemethacrylates, such as 3-(methacryloxy)propyltrimethoxysilane and3-(methacryloxy)propyl-triethoxysilane,methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane;acrylonitrile; 2-isopropenyl-2-oxazoline; styrene; α-methylstyrene;vinyltoluene; dichlorostyrene; N-vinylpyrrolidinone, vinyl acetate,methacryloxypropyltrialkoxysilanes, methacryloxymethyltrialkoxysilanesand vinyl chloride.

Mixtures of radically graftable species that comprise at least one ofthe above species may be used, with styrene/maleic anhydride andstyrene/acrylonitrile as illustrative examples.

A thermal grafting process is one method for reaction, however, othergrafting processes may be used, such as photo initiation, includingdifferent forms of radiation, e-beam, or redox radical generation.

The functionalized interpolymers disclosed herein may also be modifiedby various chain extending or cross-linking processes, including, butnot limited to peroxide-, silane-, sulfur-, radiation-, or azide-basedcure systems. A full description of the various cross-linkingtechnologies is described in U.S. Pat. No. 5,869,591 and No. 5,977,271,both of which are herein incorporated by reference in their entirety.

Suitable curing agents may include peroxides, phenols, azides,aldehyde-amine reaction products, substituted ureas, substitutedguanidines; substituted xanthates; substituted dithiocarbamates;sulfur-containing compounds, such as thiazoles, imidazoles,sulfenamides, thiuramidisulfides, paraquinonedioxime,dibenzoparaquinonedioxime, sulfur; and combinations thereof. Elementalsulfur may be used as a crosslinking agent for diene containingpolymers.

In some systems, for example, in silane grafted systems, crosslinkingmay be promoted with a crosslinking catalyst, and any catalyst that willprovide this function can be used in this invention. These catalystsgenerally include acids and bases, especially organic bases, carboxylicacids and sulfonic acids, and organometallic compounds including organictitanates, organic zirconates, and complexes or carboxylates of lead,cobalt, iron, nickel, zinc and tin. Dibutyltin dilaurate, dioctyltinmaleate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate,stannous octoate, lead naphthenate, zinc caprylate, cobalt naphthenate,and the like, are examples of suitable crosslinking catalysts.

Rather than employing a chemical crosslinking agent, crosslinking may beeffected by use of radiation or by the use of electron beam. Usefulradiation types include ultraviolet (UV) or visible radiation, beta ray,gamma rays, X-rays, or neutron rays. Radiation is believed to effectcrosslinking by generating polymer radicals which may combine andcrosslink.

Dual cure systems, which use a combination of heat, moisture cure, andradiation steps, may be effectively employed. Dual cure systems aredisclosed in U.S. Pat. No. 5,911,940 and No. 6,124,370, which areincorporated herein by reference in their entirety. For example, it maybe desirable to employ peroxide crosslinking agents in conjunction withsilane crosslinking agents; peroxide crosslinking agents in conjunctionwith radiation; or sulfur-containing crosslinking agents in conjunctionwith silane crosslinking agents.

The functionalization may also occur at the terminal unsaturated group(e.g., vinyl group) or an internal unsaturation group, when such groupsare present in the polymer. Such functionalization includes, but is notlimited to, hydrogenation, halogenation (such as chlorination),ozonation, hydroxylation, sulfonation, carboxylation, epoxidation, andgrafting reactions. Any functional groups, such as halogen, amine,amide, ester, carboxylic acid, ether, silane, siloxane, and so on, orfunctional unsaturated compounds, such as maleic anhydride, can be addedacross a terminal or internal unsaturation via known chemistry. Otherfunctionalization methods include those disclosed in the following U.S.Pat. Nos. 5,849,828, entitled, “Metalation and Functionalization ofPolymers and Copolymers;” 5,814,708, entitled, “Process for OxidativeFunctionalization of Polymers Containing Alkylstyrene;” and 5,717,039,entitled, “Functionalization of Polymers Based on Koch Chemistry andDerivatives Thereof” Each of these patents is incorporated by reference,herein, in its entirety.

Free Radical Initiators Useful for Initiating Grafting Reactions

There are several types of compounds that can initiate graftingreactions by decomposing to form free radicals, including azo-containingcompounds, carboxylic peroxyacids and peroxyesters, alkylhydroperoxides, and dialkyl and diacyl peroxides, among others. Many ofthese compounds and their properties have been described (Reference: J.Branderup, E. Immergut, E. Grulke, eds. “Polymer Handbook,” 4th ed.,Wiley, New York, 1999, Section II, pp. 1-76.). It is preferable for thespecies that is formed by the decomposition of the initiator to be anoxygen-based free radical. It is more preferable for the initiator to beselected from carboxylic peroxyesters, peroxyketals, dialkyl peroxides,and diacyl peroxides. Some of the more preferable initiators, commonlyused to modify the structure of polymers, are listed below. Also shownbelow, are the respective chemical structures and the theoreticalradical yields. The theoretical radical yield is the theoretical numberof free radicals that are generated per mole of initiator.

Theoretical Radical Initiator Name Initiator Structure Yield Benzoylperoxide

2 Lauroyl peroxide

2 Dicumyl peroxide

2 t-Butyl α-cumyl peroxide

2 Di-t-butyl peroxide

2 Di-t-amyl peroxide

2 t-Butyl peroxybenzoate

2 t-Amyl peroxybenzoate

2 1,1-Bis(t- butylperoxy)-3,3,5- trimethylcyclohexane

4 α,α′-Bis(t- butylperoxy)-1,3- diisopropylbenzene

4 α,α′-Bis(t- butylperoxy)-1,4- diisopropylbenzene

4 2,5-Bis(t- butylperoxy)-2,5- dimethylhexane

4 2,5-Bis(t- butylperoxy)-2,5-dimethyl- 3-hexyne

4

Maleic Anhydride Functionalized Olefin Interpolymers

The multi-block olefin interpolymers disclosed above may be modified by,for example, grafting with maleic anhydride. The grafted maleicanhydride olefin interpolymer may or may not contain small amounts ofhydrolysis product and/or other derivatives. In one embodiment, thegrafted maleic anhydride olefin interpolymers have a molecular weightdistribution from about 1 to 7, preferably from 1.5 to 6, and morepreferably from 2 to 5. All individual values and subranges from about 1to 7 are included herein and disclosed herein.

In another embodiment, the grafted maleic anhydride olefin interpolymershave density from 0.855 g/cc to 0.955 g/cc, preferably from 0.86 g/cc to0.90 g/cc, and more preferably from 0.865 g/cc to 0.895 g/cc. Allindividual values and subranges from 0.84 g/cc to 0.955 g/cc areincluded herein and disclosed herein.

In another embodiment, the amount of maleic anhydride used in thegrafting reaction is less than, or equal to, 10 phr (parts per hundred,based on the weight of the olefin interpolymer), preferably less than 5phr; and more preferably from 0.5 to 10 phr, and even more preferablyfrom 0.5 to 5 phr. All individual values and subranges from 0.05 phr to10 phr are included herein and disclosed herein.

In another embodiment, the amount of initiator used in the graftingreaction is less than, or equal to, 10 millimoles radicals per 100 gramsolefin interpolymer, preferably, less than, or equal to, 6 millimolesradicals per 100 grams olefin interpolymer, and more preferably, lessthan, or equal to, 3 millimoles radicals per 100 grams olefininterpolymer. All individual values and subranges from 0.01 millimolesto 10 millimoles radicals per 100 grams olefin interpolymer are includedherein and disclosed herein.

In another embodiment, the amount of maleic anhydride constituentgrafted on the polyolefin chain is greater than 0.05 weight percent(based on the weight of the olefin interpolymer), as determined bytitration analysis, FTIR analysis, or any other appropriate method. In afurther embodiment, this amount is greater than 0.25 weight percent, andin yet a further embodiment, this amount is greater than 0.5 weightpercent. In a preferred embodiment, 0.5 weight percent to 2.0 weightpercent of maleic anhydride is grafted. All individual values andsubranges greater than 0.05 weight percent are considered within thescope of this invention, and are disclosed herein.

The maleic anhydride, as well as many other unsaturated heteroatomcontaining species, may be grafted to the polymer by any conventionalmethod, typically in the presence of a free radical initiator, forexample the peroxide and azo classes of compounds, etc., or by ionizingradiation. Organic initiators are preferred, such as any one of theperoxide initiators, such as, dicumyl peroxide, di-tert-butyl peroxide,t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butylperoctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butyl peroxy)-3-hexyne, laurylperoxide, and tert-butyl peracetate. A suitable azo compound is2,2′-azobis(isobutyronitrile). The organic initiators have varyingreactivities at different temperatures, and may generate different typesof free radicals for grafting. One skilled in the art may select theappropriate organic initiator as needed for the grafting conditions.

The amount and type of initiator, the amount of maleic anhydride, aswell as reaction conditions, including temperature, time, shear,environment, additives, diluents, and the like, employed in the graftingprocess, may impact the final structure of the maleated polymer. Forexample, the degree of maleic anhydride/succinic anhydride, theiroligomers, and their derivatives, including hydrolysis products, graftedonto the grafted polymer may be influenced by the aforementionedconsiderations. Additionally, the degree and type of branching, and theamount of crosslinking, may also be influenced by the reactionconditions and concentrations. In general, it is preferred thatcrosslinking during the maleation process be minimized. The compositionof the base olefin interpolymer may also play a role in the finalstructure of the maleated polymer. The resulting structure, will inturn, affect the properties and use of the final product. Typically, theamount of initiator and maleic anhydride employed will not exceed that,which is determined to provide the desired level of maleation anddesired melt flow, each required for the functionalized polymer and itssubsequent use.

The grafting reaction should be performed under conditions that maximizegrafts onto the polymer backbone, and minimize side reactions, such asthe homopolymerization of the grafting agent, which is not grafted tothe olefin interpolymer. It is not unusual that some fraction of themaleic anhydride (and/or its derivatives) does not graft onto the olefininterpolymer, and it is generally desired that the unreacted graftingagent be minimized. The grafting reaction may be performed in the melt,in solution, in the solid-state, in a swollen-state, and the like. Themaleation may be performed in a wide-variety of equipments, such as, butnot limited to, twin screw extruders, single screw extruders,Brabenders, batch reactors, and the like.

Additional embodiments of the invention provide for olefin interpolymersgrafted with other carbonyl-containing compounds. In one embodiment,these grafted olefin interpolymers may have molecular weightdistributions and/or densities the same as, or similar to, thosedescribed above for the grafted maleic anhydride olefin interpolymers.In another embodiment, these grafted olefin interpolymers are preparedusing the same or similar amounts of grafting compound and initiator asthose used for the grafted maleic anhydride olefin interpolymers, asdescribed above. In another embodiment, these grafted olefininterpolymers contain the same or similar levels of grafted compound asfor the grafted maleic anhydride, as described above.

Additional carbonyl-containing compounds include, but are not limitedto, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate,dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride,tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleicanhydride, nadic anhydride, methylnadic anhydride, alkenylsuccinicanhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid,citraconic acid, crotonic acid, esters thereof, imides thereof, saltsthereof, and Diels-Alder adducts thereof.

Silane Functionalized Olefin Interpolymers

The multi-block olefin interpolymers disclosed above may be modified by,for example, grafting with at least one silane compound. The graftedsilane olefin interpolymer may or may not contain small amounts ofhydrolysis product and/or other derivatives.

In one embodiment, the silane-grafted olefin interpolymers have amolecular weight distribution from about 1 to 7, preferably from 1.5 to6, and more preferably from 2 to 5. All individual values and subrangesfrom about 1 to 7 are included herein and disclosed herein.

In another embodiment, the silane-grafted olefin interpolymers havedensity from 0.855 g/cc to 0.955 g/cc, and preferably from 0.86 g/cc to0.90 g/cc, and more preferably from 0.865 g/cc to 0.895 g/cc. Allindividual values and subranges from 0.84 g/cc to 0.955 g/cc areincluded herein and disclosed herein.

In another embodiment, the amount of silane used in the graftingreaction is greater than, or equal to, 0.05 phr (based on the amount ofthe olefin interpolymer), more preferably, from 0.5 phr to 6 phr, andeven more preferably, from 0.5 phr to 4 phr. All individual values andsubranges from 0.05 phr to 6 phr are included herein and disclosedherein.

In another embodiment, the amount of amount of initiator used in thegrafting reaction is less than, or equal to, 4 millimoles radicals per100 grams olefin interpolymer, preferably, less than, or equal to, 2millimoles radicals per 100 grams olefin interpolymer, and morepreferably, less than, or equal to, 1 millimoles radicals per 100 gramsolefin interpolymer. All individual values and subranges from 0.01millimoles to 4 millimoles radicals per 100 grams olefin interpolymerare included herein and disclosed herein.

In another embodiment, the amount of silane constituent grafted on thepolyolefin chain is greater than, or equal to, 0.05 weight percent(based on the weight of the olefin interpolymer), as determined by FTIRanalysis, or other appropriate method. In a further embodiment, thisamount is greater than, or equal to, 0.5 weight percent, and in yet afurther embodiment, this amount is greater than, or equal to, 1.2 weightpercent. In a preferred embodiment, the amount silane constituentgrafted on the olefin interpolymer is from 0.5 weight percent to 4.0weight percent. All individual values and subranges greater than 0.05weight percent are considered within the scope of this invention, andare disclosed herein.

Suitable silanes include, but are not limited to, those of the generalformula (I):

CH₂═CR—(COO)_(x)(C_(n)H_(2n))_(y)SiR′₃  (I).

In this formula, R is a hydrogen atom or methyl group; x and y are 0 or1, with the proviso that when x is 1, y is 1; n is an integer from 1 to12 inclusive, preferably 1 to 4, and each R′ independently is an organicgroup, including, but not limited to, an alkoxy group having from 1 to12 carbon atoms (e.g. methoxy, ethoxy, butoxy), an aryloxy group (e.g.phenoxy), an araloxy group (e.g. benzyloxy), an aliphatic or aromaticsiloxy group, an aromatic acyloxyl group, an aliphatic acyloxy grouphaving from 1 to 12 carbon atoms (e.g. formyloxy, acetyloxy,propanoyloxy), amino or substituted amino groups (alkylamino,arylamino), or a lower alkyl group having 1 to 6 carbon atoms.

In one embodiment, the silane compound is selected fromvinyltrialkoxysilanes, vinyltriacyloxysilanes or vinyltrichlorosilane.In addition, any silane, or mixtures of silanes, which will effectivelygraft to, and/or crosslink, the olefin interpolymers can be used in thepractice of this invention. Suitable silanes include unsaturated silanesthat comprise both an ethylenically unsaturated hydrocarbyl group, suchas a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl orγ-(meth)acryloxy allyl group, and a hydrolyzable group, such as, ahydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino group, or ahalide. Examples of hydrolyzable groups include methoxy, ethoxy,formyloxy, acetoxy, proprionyloxy, chloro, and alkyl or arylaminogroups. Preferred silanes are the unsaturated alkoxy silanes which canbe grafted onto the polymer. These silanes and their method ofpreparation are more fully described in U.S. Pat. No. 5,266,627 toMeverden, et al., which is incorporated herein, in its entirety, byreference. Preferred silanes include vinyltrimethoxysilane,vinyltriethoxysilane, 3-(trimethoxysilyl)propyl methacrylate(γ-(meth)acryloxypropyl trimethoxysilane), and mixtures thereof.

The silane can be grafted to the polymer by any conventional method,typically in the presence of a free radical initiator, for exampleperoxides and azo compounds, etc., or by ionizing radiation. Organicinitiators are preferred, such as any one of the peroxide initiators,for example, dicumyl peroxide, di-tert-butyl peroxide, t-butylperbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate,methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, lauryl peroxide, and tert-butyl peracetate. A suitableazo compound is 2,2′-azobis(isobutyronitrile).

The amount of initiator and silane employed will affect the finalstructure of the silane grafted polymer, such as, for example, thedegree of grafting in the grafted polymer and the degree of crosslinkingin the cured polymer. The resulting structure, will in turn, affect thephysical and mechanical properties of the final product. Typically, theamount of initiator and silane employed will not exceed that which isdetermined to provide the desired level of crosslinking, and theresulting properties in the polymer.

The grafting reaction should be performed under conditions that maximizegrafts onto the polymer backbone, and minimize side reactions, such asthe homopolymerization of grafting agent, which is not grafted to thepolymer. Some silane agents undergo minimal or no homopolymerization,due to steric features in the molecular structure, low reactivity and/orother reasons.

Cure (crosslinking) of a silanated graft is promoted with a crosslinkingcatalyst, and any catalyst that will effectively promote thecrosslinking of the particular grafted silane can be used. Thesecatalysts generally include acids and bases, and organometalliccompounds, including organic titanates, organic zirconates, andcomplexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin.

Dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate,dibutyltin dioctoate, stannous acetate, stannous octoate, leadnaphthenate, zinc caprylate, cobalt naphthenate, and the like, can beused. The amount of catalyst will depend on the particular system atissue.

In certain embodiments of the claimed invention, dual crosslinkingsystems, which use a combination of radiation, heat, moisture andcrosslinking steps, may be effectively employed. For instance, it may bedesirable to employ peroxide crosslinking agents in conjunction withsilane crosslinking agents, peroxide crosslinking agents in conjunctionwith radiation, or sulfur-containing crosslinking agents in conjunctionwith silane crosslinking agents. Dual crosslinking systems aredisclosed, and claimed in, U.S. Pat. Nos. 5,911,940 and 6,124,370, theentire contents of both are herein incorporated by reference.

The silane grafted interpolymers of the present invention are oftenuseful in adhesive compositions. In this regard the functionalizedinterpolymers may be characterized by, for example, a Peel AdhesionFailure Temperature (PAFT) of greater than, or equal to, 110° F. (43°C.), or a Shear Adhesion Failure Temperature (SAFT) of greater than, orequal to, 140° F. (60° C.); or both wherein PAFT and SAFT are measuredas follows:

Shear Adhesion Failure Temperature (SAFT)

Shear adhesion failure temperature (SAFT) of each sample was measuredaccording to ASTM D 4498 with a 500 gram weight in the shear mode. Thetests were started at room temperature (25° C./77° F.) and the oventemperature was ramped at an average rate of 0.5° C./minute. Thetemperature at which the specimen failed was recorded. This measurementwas used as an indication of the heat resistance of the compositionwhich is important for shipping.

Peel Adhesion Failure Temperature (PAFT)

Peel adhesion failure temperature (PAFT) was tested according to ASTM D4498 with a 100 gram weight in the peel mode. The tests were started atroom temperature (25° C./77° F.) and the temperature was increased at anaverage rate of 0.5° C./minute.

In addition, if the silane-grafted interpolymer is to be employed in,for example, an adhesive composition, it is often preferable that thesilane-grafted ethylene/α-olefin polymer have a molecular weightdistribution (Mw/Mn) from about 1 to about 3.5 and/or a number averagemolecular weight from 5,000 to 25,000.

Azide Modification

The multi-block olefin interpolymers disclosed above may be modified by,for example, azide modification. Compounds having at least two sulfonylazide groups capable of C—H insertion under reaction conditions arereferred to herein as coupling agents. For the purpose of the invention,the poly(sulfonyl azide) is any compound having at least two sulfonylazide groups reactive with a polyolefin under reaction conditions.Preferably the poly(sulfonyl azide)s have a structure X—R—X wherein eachX is SO₂N₃ and R represents an unsubstituted or inertly substitutedhydrocarbyl, hydrocarbyl ether or silicon-containing group, preferablyhaving sufficient carbon, oxygen or silicon, preferably carbon, atoms toseparate the sulfonyl azide groups sufficiently to permit a facilereaction between the polyolefin and the sulfonyl azide, more preferablyat least 1, more preferably at least 2, most preferably at least 3carbon, oxygen or silicon, preferably carbon, atoms between functionalgroups. While there is no critical limit to the length of R, each Radvantageously has at least one carbon or silicon atom between X's andpreferably has less than about 50, more preferably less than about 30,most preferably less than about 20 carbon, oxygen or silicon atoms.Within these limits, larger is better for reasons including thermal andshock stability. When R is straight-chain alkyl hydrocarbon, there arepreferably less than 4 carbon atoms between the sulfonyl azide groups toreduce the propensity of the nitrene to bend back and react with itself.Silicon containing groups include silanes and siloxanes, preferablysiloxanes. The term inertly substituted refers to substitution withatoms or groups which do not undesirably interfere with the desiredreaction(s) or desired properties of the resulting coupled polymers.Such groups include fluorine, aliphatic or aromatic ether, siloxane aswell as sulfonyl azide groups when more than two polyolefin chains areto be joined. Suitable structures include R as aryl, alkyl, arylalkaryl, arylalkyl silane, siloxane or heterocyclic, groups and othergroups which are inert and separate the sulfonyl azide groups asdescribed. More preferably R includes at least one aryl group betweenthe sulfonyl groups, most preferably at least two aryl groups (such aswhen R is 4,4′ diphenylether or 4,4′-biphenyl). When R is one arylgroup, it is preferred that the group have more than one ring, as in thecase of naphthylene bis(sulfonyl azides). Poly(sulfonyl)azides includesuch compounds as 1,5-pentane bis(sulfonyl azide), 1,8-octanebis(sulfonyl azide), 1,10-decane bis(sulfonyl azide), 1,10-octadecanebis(sulfonyl azide), 1-octyl-2,4,6-benzene tris(sulfonyl azide),4,4′-diphenyl ether bis(sulfonyl azide),1,6-bis(4′-sulfonazidophenyl)hexane, 2,7-naphthalene bis(sulfonylazide), and mixed sulfonyl azides of chlorinated aliphatic hydrocarbonscontaining an average of from 1 to 8 chlorine atoms and from about 2 to5 sulfonyl azide groups per molecule, and mixtures thereof. Preferredpoly(sulfonyl azide)s include oxy-bis(4-sulfonylazidobenzene),2,7-naphthalene bis(sulfonyl azido), 4,4′-bis(sulfonyl azido)biphenyl,4,4′-diphenyl ether bis(sulfonyl azide) and bis(4-sulfonylazidophenyl)methane, and mixtures thereof.

Sulfonyl azides are conveniently prepared by the reaction of sodiumazide with the corresponding sulfonyl chloride, although oxidation ofsulfonyl hydrazines with various reagents (nitrous acid, dinitrogentetraoxide, nitrosonium tetrafluoroborate) has been used.

Polyfunctional compounds capable of insertions into C—H bonds alsoinclude carbene-forming compounds such as salts of alkyl and arylhydrazones and diazo compounds, and nitrene-forming compounds such asalkyl and aryl azides (R—N3), acyl azides (R—C(O)N3), azidoformates(R—O—C(O)—N3), sulfonyl azides (R—SO2-N3), phosphoryl azides((RO)2-(PO)—N3), phosphinic azides (R2-P(O)—N3) and silyl azides(R3-Si—N3) Some of the coupling agents of the invention are preferredbecause of their propensity to form a greater abundance ofcarbon-hydrogen insertion products. Such compounds as the salts ofhydrazones, diazo compounds, azidoformates, sulfonyl azides, phosphorylazides, and silyl azides are preferred because they form stablesingle-state electron products (carbenes and nitrenes) which carry outefficient carbon-hydrogen insertion reactions, rather thansubstantially 1) rearranging via such mechanisms as the Curtius-typerearrangement, as is the case with acyl azides and phosphinic azides, or2) rapidly converting to the triplet-state electron configuration whichpreferentially undergoes hydrogen atom abstraction reactions, which isthe case with alkyl and aryl azides. Also, selection from among thepreferred coupling agents is conveniently possible because of thedifferences in the temperatures at which the different classes ofcoupling agents are converted to the active carbene or nitrene products.For example, those skilled in the art will recognize that carbenes areformed from diazo compounds efficiently at temperatures less than 100°C., while salts of hydrazones, azidoformates and the sulfonyl azidecompounds react at a convenient rate at temperatures above 100° C., upto temperatures of about 200° C. (By convenient rates it is meant thatthe compounds react at a rate that is fast enough to make commercialprocessing possible, while reacting slowly enough to allow adequatemixing and compounding to result in a final product with the couplingagent adequately dispersed and located substantially in the desiredposition in the final product. Such location and dispersion may bedifferent from product to product depending on the desired properties ofthe final product.) Phosphoryl azides may be reacted at temperatures inexcess of 180° C. up to about 300° C., while silyl azides reactpreferentially at temperatures of from about 250° C. to 400° C.

To modify rheology, also referred to herein as “to couple,” thepoly(sulfonyl azide) is used in a rheology modifying amount, that is anamount effective to increase the low-shear viscosity (at 0.1 rad/sec) ofthe polymer preferably at least about 5 percent as compared with thestarting material polymer, but less than a crosslinking amount, that isan amount sufficient to result in at least about 10 weight percent gelas measured by ASTM D2765-procedure A. While those skilled in the artwill recognize that the amount of azide sufficient to increase the lowshear viscosity and result in less than about 10 weight percent gel willdepend on molecular weight of the azide used and polymer the amount ispreferably less than about 5 percent, more preferably less than about 2percent, most preferably less than about 1 weight percent poly(sulfonylazide) based on total weight of polymer when the poly(sulfonyl azide)has a molecular weight of from about 200 to about 2000. To achievemeasurable rheology modification, the amount of poly(sulfonyl azide) ispreferably at least about 0.01 weight percent, more preferably at leastabout 0.05 weight percent, most preferably at least about 0.10 weightpercent based on total polymer. If crosslinking is desired than theazide will typically be used in a crosslinking amount.

For rheology modification and/or crosslinking, the sulfonyl azide isadmixed with the polymer and heated to at least the decompositiontemperature of the sulfonyl azide. By decomposition temperature of theazide it is meant that temperature at which the azide converts to thesulfonyl nitrene, eliminating nitrogen and heat in the process, asdetermined by differential scanning calorimetry (DSC). The poly(sulfonylazide) begins to react at a kinetically significant rate (convenient foruse in the practice of the invention) at temperatures of about 130° C.and is almost completely reacted at about 160° C. in a DSC (scanning at10° C./min). Accelerated Rate Calorimetry (ARC) (scanning at 2° C./hr)shows onset of decomposition is about 100° C. Extent of reaction is afunction of time and temperature. At the low levels of azide used in thepractice of the invention, the optimal properties are not reached untilthe azide is essentially fully reacted. Temperatures for use in thepractice of the invention are also determined by the softening or melttemperatures of the polymer starting materials. For these reasons, thetemperature is advantageously greater than about 90° C., preferablygreater than about 120° C., more preferably greater than about 150° C.,most preferably greater than 180° C.

Preferred times at the desired decomposition temperatures are times thatare sufficient to result in reaction of the coupling agent with thepolymer(s) without undesirable thermal degradation of the polymermatrix. Preferred reaction times in terms of the half life of thecoupling agent, that is the time required for about half of the agent tobe reacted at a preselected temperature, which half life is determinableby DSC is about 5 half lives of the coupling agent. In the case of abis(sulfonyl azide), for instance, the reaction time is preferably atleast about 4 minutes at 200° C.

Admixing of the polymer and coupling agent is conveniently accomplishedby any means within the skill in the art. Desired distribution isdifferent in many cases, depending on what rheological properties are tobe modified. In a homopolymer it is desirable to have as homogeneous adistribution as possible, preferably achieving solubility of the azidein the polymer melt. In a blend it is desirable to have low solubilityin one or more of the polymer matrices such that the azide ispreferentially in one or the other phase, or predominantly in theinterfacial region between the two phases.

Preferred processes include at least one of (a) dry blending thecoupling agent with the polymer, preferably to form a substantiallyuniform admixture and adding this mixture to melt processing equipment,e.g. a melt extruder to achieve the coupling reaction, at a temperatureat least the decomposition temperature of the coupling agent; (b)introducing, e.g. by injection, a coupling agent in liquid form, e.g.dissolved in a solvent therefor or in a slurry of coupling agent in aliquid, into a device containing polymer, preferably softened, molten ormelted polymer, but alternatively in particulate form, in solution ordispersion, more preferably in melt processing equipment; (c) forming afirst admixture of a first amount of a first polymer and a couplingagent, advantageously at a temperature less than about the decompositiontemperature of the coupling agent, preferably by melt blending, and thenforming a second admixture of the first admixture with a second amountof a second polymer (for example a concentrate of a coupling agentadmixed with at least one polymer and optionally other additives, isconveniently admixed into a second polymer or combination thereofoptionally with other additives, to modify the second polymer(s)); (d)feeding at least one coupling agent, preferably in solid form, morepreferably finely comminuted, e.g. powder, directly into softened ormolten polymer, e.g. in melt processing equipment, e.g. in an extruder;or combinations thereof. Among processes (a) through (d), processes (b)and (c) are preferred, with (c) most preferred. For example, process (c)is conveniently used to make a concentrate with a first polymercomposition having a lower melting temperature, advantageously at atemperature below the decomposition temperature of the coupling agent,and the concentrate is melt blended into a second polymer compositionhaving a higher melting temperature to complete the coupling reaction.Concentrates are especially preferred when temperatures are sufficientlyhigh to result in loss of coupling agent by evaporation or decompositionnot leading to reaction with the polymer, or other conditions wouldresult that effect. Alternatively, some coupling occurs during theblending of the first polymer and coupling agent, but some of thecoupling agent remains unreacted until the concentrate is blended intothe second polymer composition. Each polymer or polymer compositionincludes at least one homopolymer, copolymer, terpolymer, orinterpolymer and optionally includes additives within the skill in theart. When the coupling agent is added in a dry form it is preferred tomix the agent and polymer in a softened or molten state below thedecomposition temperature of the coupling agent then to heat theresulting admixture to a temperature at least equal to the decompositiontemperature of the coupling agent.

The term “melt processing” is used to mean any process in which thepolymer is softened or melted, such as extrusion, pelletizing, molding,thermoforming, film blowing, compounding in polymer melt form, fiberspinning, and the like.

The polyolefin(s) and coupling agent are suitably combined in any mannerwhich results in desired reaction thereof, preferably by mixing thecoupling agent with the polymer(s) under conditions which allowsufficient mixing before reaction to avoid uneven amounts of localizedreaction then subjecting the resulting admixture to heat sufficient forreaction. Preferably, a substantially uniform admixture of couplingagent and polymer is formed before exposure to conditions in which chaincoupling takes place. A substantially uniform admixture is one in whichthe distribution of coupling agent in the polymer is sufficientlyhomogeneous to be evidenced by a polymer having a melt viscosity aftertreatment according to the practice of the invention at least one of (a)higher at low angular frequency (e.g. 0.1 rad/sec) or (b) lower athigher angular frequency (e.g. 100 rad/sec) than that of the samepolymer which has not been treated with the coupling agent but has beensubjected to the same shear and thermal history. Thus, preferably, inthe practice of the invention, decomposition of the coupling agentoccurs after mixing sufficient to result in a substantially uniformadmixture of coupling agent and polymer. This mixing is preferablyattained with the polymer in a molten or melted state, that is above thecrystalline melt temperature, or in a dissolved or finely dispersedcondition rather than in a solid mass or particulate form. The molten ormelted form is more preferred to insure homogeneity rather thanlocalized concentrations at the surface.

Any equipment is suitably used, preferably equipment which providessufficient mixing and temperature control in the same equipment, butadvantageously practice of the invention takes place in such devices asan extruder or a static polymer mixing devise such as a Brabenderblender. The term extruder is used for its broadest meaning to includesuch devices as a device which extrudes pellets or pelletizer.Conveniently, when there is a melt extrusion step between production ofthe polymer and its use, at least one step of the process of theinvention takes place in the melt extrusion step. While it is within thescope of the invention that the reaction take place in a solvent orother medium, it is preferred that the reaction be in a bulk phase toavoid later steps for removal of the solvent or other medium. For thispurpose, a polymer above the crystalline melt temperature isadvantageous for even mixing and for reaching a reaction temperature(the decomposition temperature of the sulfonyl azide).

In a preferred embodiment the process of the present invention takesplace in a single vessel, that is mixing of the coupling agent andpolymer takes place in the same vessel as heating to the decompositiontemperature of the coupling agent. The vessel is preferably a twin-screwextruder, but is also advantageously a single-screw extruder, a batchmixer, or a static mixing zone for mixing polymer at the back end of aproduction process. The reaction vessel more preferably has at least twozones of different temperatures into which a reaction mixture wouldpass, the first zone advantageously being at a temperature at least thecrystalline melt temperature or the softening temperature of thepolymer(s) and preferably less than the decomposition temperature of thecoupling agents and the second zone being at a temperature sufficientfor decomposition of the coupling agent. The first zone is preferably ata temperature sufficiently high to soften the polymer and allow it tocombine with the coupling agent through distributive mixing to asubstantially uniform admixture.

For polymers that have softening points above the coupling agentdecomposition temperature (preferably greater than 200° C.), andespecially when incorporation of a lower melting polymer (such as in aconcentrate) is undesirable, the preferred embodiment for incorporationof coupling agent is to solution blend the coupling agent in solution oradmixture into the polymer, to allow the polymer to imbibe (absorb oradsorb at least some of the coupling agent), and then to evaporate thesolvent. After evaporation, the resulting mixture is extruded. Thesolvent is preferably a solvent for the coupling agent, and morepreferably also for the polymer when the polymer is soluble such as inthe case of polycarbonate. Such solvents include polar solvents such asacetone, THF (tetrahydrofuran) and chlorinated hydrocarbons such asmethylene chloride. Alternatively other non-polar compounds such asmineral oils in which the coupling agent is sufficiently miscible todisperse the coupling agent in a polymer, are used.

To avoid the extra step and resultant cost of re-extrusion and to insurethat the coupling agent is well blended into the polymer, in alternativepreferred embodiments it is preferred that the coupling agent be addedto the post-reactor area of a polymer processing plant. For example, ina slurry process of producing polyethylene, the coupling agent is addedin either powder or liquid form to the powdered polyethylene after thesolvent is removed by decantation and prior to the drying anddensification extrusion process. In an alternative embodiment, whenpolymers are prepared, in a gas phase process, the coupling agent ispreferably added in either powder or liquid form to the powderedpolyethylene before the densification extrusion. In an alternativeembodiment when a polymer is made in a solution process, the couplingagent is preferably added to the polymer melt stream afterdevolatilization and before the pelletizing extrusion process.

Practice of the process of the invention to rheology modify polymersyields rheology modified or chain coupled polymers, that is the polymerswhich have sulfonamide, amine, alkyl-substituted or aryl-substitutedcarboxamide, alkyl-substituted or aryl-substituted phosphoramide,alkyl-substituted or aryl-substituted methylene coupling betweendifferent polymer chains. Resulting compounds Advantageously show higherlow shear viscosity than the original polymer due to coupling of longpolymer chains to polymer backbones. Broad molecular weight monomodaldistribution polymers (MWD of 3.0 and greater) and gel levels less than10 percent as determined by xylene extraction show less improvement thanthe dramatic effect noted in narrow MWD polymer (e.g. MWD=about 2.0)with gel less than 10 percent as determined by xylene extraction.Alternatively, those skilled in the art will recognize that it ispossible to prepare polymers with broader polydispersity (e.g. MWDgreater than about 2.0) by blending polymers of low polydispersity,either by post-reactor compounding, or by preparing the polymers in amulti-reactor configuration wherein the conditions of each reactor arecontrolled to provide a polymer with the desired molecular weight andMWD for each specific component resin of the final product.

Rheology modification leads to polymers which have controlledrheological properties, specifically improved melt strength as evidencedby increased low shear viscosity, better ability to hold oil, improvedscratch and mar resistance, improved tackiness, improved green strength(melt), higher orientation in high shear and high extensional processessuch as injection molding, film extrusion (blown and cast), calendaring,rotomolding, fiber production, profile extrusion, foams, and wire andcable insulation as measured by tan delta as described hereinafter,elasticity by viscosity at 0.1 rad/sec and 100 rad/sec, respectively. Itis also believed that this process can be used to produce dispersionshaving improved properties of higher low shear viscosity than theunmodified polymer as measured by Dynamic Mechanical Spectroscopy (DMS).

Rheology modified polymers are useful as large blow molded articles dueto the higher low shear viscosity than unmodified polymer and themaintenance of the high shear viscosity for processability as indicatedby high shear viscosity, foams for stable cell structure as measured bylow shear viscosity, blown film for better bubble stability as measuredby low shear viscosity, fibers for better spinnability as measured byhigh shear viscosity, cable and wire insulation for green strength toavoid sagging or deformation of the polymer on the wire as measured bylow shear viscosity which are aspects of the invention.

Polymers rheology modified according to the practice of the inventionare superior to the corresponding unmodified polymer starting materialsfor these applications due to the elevation of viscosity, of preferablyat least about 5 percent at low shear rates (0.1 rad/sec), sufficientlyhigh melt strengths to avoid deformation during thermal processing (e.g.to avoid sag during thermoforming or profile extrusion) or to achievebubble strength during blow molding, and sufficiently low high shearrate viscosities to facilitate molding and extrusion. Compositionscomprising rheology modified multi-block copolymer preferably have aviscosity ratio (ratio of shear viscosity at 0.1 rad/sec to shearviscosity at 100 rad/sec measured at 190° C.) of greater than 5,preferably greater than 10 and more preferably greater than 20, and mostpreferably greater than 30. These rheological attributes enable fasterfilling of injection molds at high rates than the unmodified startingmaterials, the setup of foams (stable cell structure) as indicated byformation of lower density closed cell foam, preferably with highertensile strength, insulation properties, and/or compression set thanattained in the use of coupling or rheology modification using couplingagents which generate free radicals, because of high melt viscosity.Advantageously toughness and tensile strength of the starting materialis maintained. Additionally, compression set (particularly hightemperature such as about 70° C. or higher) property is improved.

Polymers resulting from the practice of the invention are different fromthose resulting from practice of prior art processes as shown in CA797,917. The polymers of the present invention show improved meltelasticity, that is higher tan delta as measured by DMS, betterdrawability, that is higher melt strength as measured by melt tension,less swelling as measured by blow molding die swell, and less shrinkageas measured by mold shrinkage than the unmodified polymer and the broadMWD (greater than about 3.0 Mw/Mn) counterpart in thermoforming andlarge part blow molding.

Compositions and Blends Containing the Functionalized OlefinInterpolymers

The functionalized olefin interpolymers of the invention may be blendedwith one or more other polymers to improve the performance,processibility and/or cost of the resultant blend.

Suitable polymers for blending with the functionalized olefininterpolymers of the invention, include non-functionalized multi-blockcopolymers, other functionalized multi-block copolymers, thermoplasticand non-thermoplastic polymers, including natural and syntheticpolymers. Exemplary polymers for blending include polypropylene, (bothimpact modifying polypropylene, isotactic polypropylene, atacticpolypropylene, and random ethylene/propylene copolymers), various typesof polyethylene (PE), including high pressure, free-radical Low DensityPolyethylene (LDPE), Ziegler Natta Linear Low Density Polyethylene(LLDPE), metallocene PE, including multiple reactor PE (“in reactor”blends of Ziegler-Natta PE and metallocene PE, such as productsdisclosed in U.S. Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045,5,869,575, and 6,448,341, ethylene-vinyl acetate (EVA), ethylene/vinylalcohol copolymers, polystyrene, impact modified polystyrene,acrylonitrile-butadiene-styrene (ABS), styrene/butadiene blockcopolymers and hydrogenated derivatives thereof (SBS and SEBS), andthermoplastic polyurethanes. Homogeneous polymers such as olefinplastomers and elastomers, ethylene and propylene-based copolymers (forexample polymers available under the trade designation VERSIFY™,available from The Dow Chemical Company, and VISTAMAXX™, available fromExxonMobil, can also be useful as components in blends comprising thefunctionalized interpolymers.

Additional polymers for blending include, but are not limited to,polyamides, polyesters, polycarbonate, other engineering thermoplastics,polyvinyl alcohol, polyvinylidene chloride, polyvinyl chloride, andnatural products, such as cellulose and wool fibers. Suitable polyamidesinclude, but are not limited to, aliphatic polyamides, such aspolycaprolactam (nylon 6), poly(hexamethylene adipamide) (nylon 6,6),poly(hexamethylene sebacamide); and aromatic polyamides (orpolyaramides). Suitable polyesters include, but are not limited to,poly(ethylene terephthalate) (PET) and poly(butylene terephthalate)(PBT). Thermoset systems such as epoxies, unsaturated polyesters, andthe like, may have the functionalized multi-block polymers blended intothem prior to curing or during the curing of the thermoset system.

In one embodiment, the invention provides thermoplastic compositions,comprising a thermoplastic matrix polymer, especially a polyamide,polyester or a polyolefin, such as polypropylene, and a dispersed phase,containing a core-shell or core-multiple shell morphology. The shellcomprising a functionalized multi-block interpolymer according to theinvention, and the core comprising the multi-block unfunctionalizedinterpolymer and/or other types of polyolefins.

The base multi-block unfunctionalized interpolymer may also form innercore-shell type particles having hard crystalline or semi-crystallineblocks in the form of a “core,” surrounded by soft or elastomericblocks, forming a “shell” around the occluded domains of hard polymer.These particles may be formed and dispersed within the matrix polymer bythe forces incurred during melt compounding or blending.

This desired core-shell or core-multiple shell morphologies may resultfrom, or be enhanced by, chemical interactions between thefunctionalized moiety of the base interpolymer and the matrix resin.These chemical interactions may result in covalent bonds or noncovalentassociations. For example, maleic anhydride grafts can form amidelinkages with terminal amines of a polyamide, or form ester linkageswith terminal hydroxyls of a polyester. The chemical interactions mayalso arise from enhanced associations between the functional groups ofthe functionalized olefin interpolymers and chemical moieties in thematrix polymer. Such associations include, but are not limited to,dipole-dipole interactions, hydrogen bonding, hydrophilic interactionsand hydrophobic interactions.

Additional blends include thermoplastic polyolefin blends, thermoplasticelastomer blends, thermoplastic vulcanisites and styrenic polymerblends. Thermoplastic polyolefin blends and thermoplastic vulcanisitesmay be prepared by combining the functionalized multi-block polymers,including unsaturated derivatives thereof, with an optional rubber,including conventional block copolymers, especially an SBS blockcopolymer, and optionally, a crosslinking or vulcanizing agent(including peroxides and/or other coagents). The thermoplasticpolyolefin blends are generally prepared by blending the functionalizedmulti-block copolymers with a polyolefin, and optionally a crosslinkingor vulcanizing agent. The foregoing blends may be used in forming amolded object, and optionally crosslinking the resulting molded article.A similar procedure, using different components, has been previouslydisclosed in U.S. Pat. No. 6,797,779, incorporated herein by reference.Suitable conventional block copolymers desirably possess a Mooneyviscosity (ML₁₊₄@100° C.) in the range from 10 to 135, more preferablyfrom 25 to 100, and most preferably from 30 to 80. Suitable polyolefinsinclude linear or low density polyethylene, polypropylene (includingatactic, isotactic, syndiotactic and impact modified versions thereof)and poly(4-methyl-1-pentene). Suitable styrenic polymers includepolystyrene, rubber modified polystyrene (HIPS), styrene/acrylonitrilecopolymers (SAN), rubber modified SAN (ABS or AES) and styrene maleicanhydride copolymers.

Blends, as described herein, may be prepared by mixing or kneading therespective components at a temperature around, or above, the melt pointtemperature of one or both of the components. For some functionalizedmulti-block copolymers, this temperature may be above 90° C., mostgenerally above 100° C., and most preferably above 110° C. Typicalpolymer mixing or kneading equipment, capable of reaching the desiredtemperatures and capable of melt plastifying the mixture, may beemployed. These include mills, kneaders, extruders (both single screwand twin-screw), Banbury mixers, calenders, and the like. The sequenceof mixing, and method, may depend on the final composition. Acombination of Banbury batch mixers and continuous mixers may also beemployed, such as a Banbury mixer, followed by a mill mixer, followed byan extruder.

The blend compositions may contain processing oils, plasticizers, andprocessing aids. Rubber processing oils have a certain ASTM designation,and paraffinic, napthenic or aromatic process oils are all suitable foruse. Generally from 0 to 150 parts, more preferably 0 to 100 parts, andmost preferably from 0 to 50 parts of oil per 100 parts of total polymerare employed. Higher amounts of oil may tend to improve the processingof the resulting product at the expense of some physical properties.Additional processing aids include conventional waxes, fatty acid salts,such as calcium stearate or zinc stearate, (poly)alcohols includingglycols, (poly)alcohol ethers, including glycol ethers, (poly)esters,including (poly)glycol esters, and metal salt-, especially Group 1 or 2metal or zinc-, salt derivatives thereof.

Compositions, including thermoplastic blends according to the inventionmay also contain anti-ozonants or anti-oxidants that are known to arubber chemist of ordinary skill. The anti-ozonants may be physicalprotectants, such as waxy materials that come to the surface and protectthe part from oxygen or ozone, or they may be chemical protectors thatreact with oxygen or ozone. Suitable chemical protectors includestyrenated phenols, butylated octylated phenol, butylateddi(dimethylbenzyl)phenol, p-phenylenediamines, butylated reactionproducts of p-cresol and dicyclopentadiene (DCPD), polyphenolicantioxidants, hydroquinone derivatives, quinoline, diphenyleneantioxidants, thioester antioxidants, and blends thereof. Somerepresentative trade names of such products are Wingstay™ S antioxidant,Polystay™ 100 antioxidant, Polystay™ 100 AZ antioxidant, Polystay™ 200antioxidant, Wingstay™ L antioxidant, Wingstay™ LHLS antioxidant,Wingstay™ K antioxidant, Wingstay™ 29 antioxidant, Wingstay™ SN-1antioxidant, and Irganox™ antioxidants. In some applications, theanti-oxidants and anti-ozonants used, will preferably be non-stainingand non-migratory.

For providing additional stability against UV radiation, hindered aminelight stabilizers (HALS) and UV absorbers may be also used. Suitableexamples include Tinuvin™ 123, Tinuvin™ 144, Tinuvin™ 622, Tinuvin™ 765,Tinuvin™ 770, and Tinuvin™ 780, available from Ciba SpecialityChemicals, and Chemisorb™ T944, available from Cytex Plastics, HoustonTex., USA. A Lewis acid may be additionally included with a HALScompound in order to achieve superior surface quality, as disclosed inU.S. Pat. No. 6,051,681.

For some compositions, an additional mixing process may be employed topre-disperse the anti-oxidants, anti-ozonants, carbon black, UVabsorbers, and/or light stabilizers, to form a masterbatch, andsubsequently to form polymer blends therefrom.

Suitable crosslinking agents (also referred to as curing or vulcanizingagents), for use herein include sulfur based, peroxide based, orphenolic based compounds. Examples of the foregoing materials are foundin the art, including in U.S. Pat. Nos. 3,758,643, 3,806,558, 5,051,478,4,104,210, 4,130,535, 4,202,801, 4,271,049, 4,340,684, 4,250,273,4,927,882, 4,311,628 and 5,248,729, all incorporated herein byreference.

When sulfur based curing agents are employed, accelerators and cureactivators may be used as well. Accelerators are used to control thetime and/or temperature required for dynamic vulcanization, and toimprove the properties of the resulting cross-linked article. In oneembodiment, a single accelerator or primary accelerator is used. Theprimary accelerator(s) may be used in total amounts ranging from about0.5 to about 4, preferably about 0.8 to about 1.5, phr, based on totalcomposition weight. In another embodiment, combinations of a primary anda secondary accelerator might be used, with the secondary acceleratorbeing used in smaller amounts, such as from about 0.05 to about 3 phr,in order to activate, and to improve the properties of the curedarticle. Combinations of accelerators generally produce articles havingproperties that are somewhat better than those produced by use of asingle accelerator. In addition, delayed action accelerators may beused, which are not affected by normal processing temperatures, yetproduce a satisfactory cure at ordinary vulcanization temperatures.Vulcanization retarders might also be used.

Suitable types of accelerators that may be used in the present inventionare amines, disulfides, guanidines, thioureas, thiazoles, thiurams,sulfenamides, dithiocarbamates and xanthates. Preferably, the primary,accelerator is a sulfenamide. If a second accelerator is used, thesecondary accelerator is preferably a guanidine, dithiocarbamate orthiuram compound. Certain processing aids and cure activators, such asstearic acid and ZnO may also be used. When peroxide based curing agentsare used, co-activators or coagents may be used in combinationtherewith. Suitable coagents include trimethylolpropane triacrylate(TMPTA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate(TAC), triallyl isocyanurate (TAIC), among others. Use of peroxidecrosslinkers and optional coagents, used for partial or complete dynamicvulcanization, are known in the art, and disclosed for example in thepublication, “Peroxide Vulcanization of Elastomer”, Vol. 74, No 3,July-August 2001.

When the functionalized multi-block copolymer containing composition isat least partially crosslinked, the degree of crosslinking may bemeasured by dissolving the composition in a solvent for specifiedduration, and calculating the percent gel or unextractable component.The percent gel normally increases with increasing crosslinking levels.For cured articles according to the invention, the percent gel contentis desirably in the range from 5 to 100 percent.

The functionalized multi-block copolymers of the invention, as well asblends thereof, may possess improved processability compared to priorart compositions, due to lower melt viscosity. Thus, the composition orblend may also from an improved surface appearance, especially whenformed into a molded or extruded article. At the same time, the presentcompositions and blends thereof may also possess improved melt strengthproperties, thereby allowing the present functionalized multi-blockcopolymers and blends thereof, especially TPO blends, to be usefullyemployed in foam and thermoforming applications where melt strength iscurrently inadequate.

Thermoplastic compositions and thermoset compositions, each containingfunctionalized multi-block copolymer, according to the invention, mayalso contain organic or inorganic fillers or other additives such asstarch, talc, calcium carbonate, glass fibers, polymeric fibers(including nylon, rayon, cotton, polyester, and polyaramide), metalfibers, flakes or particles, expandable layered silicates, phosphates orcarbonates, such as clays, mica, silica, alumina, aluminosilicates oraluminophosphates, carbon whiskers, carbon fibers, nanoparticlesincluding nanotubes, wollastonite, graphite, zeolites, and ceramics,such as silicon carbide, silicon nitride or titanias. Silane basedcoupling agents or other coupling agents may also be employed for betterfiller bonding.

The thermoplastic compositions of this invention, including theforegoing blends, may be processed by conventional molding techniques,such as injection molding, extrusion molding, thermoforming, slushmolding, over molding, insert molding, blow molding, and othertechniques. Films, including multi-layer films, may be produced by castor tentering processes, including blown film processes.

EXAMPLES OF THE PRESENT INVENTION Maleation of Base Polymers BasePolymers

A description of the base polymers used in the examples below is shownin the Base Polymers Table. The comonomer in each base polymer was1-octene. In the studies that follow, the grafted-EO885, grafted-EO870and grafted-EO875 serve as comparative examples. The grafted-Multi-blockR6; grafted-Multi-block R9, grafted-Multi-block R21 andgrafted-Multi-block R22 are examples of the inventive resins.

Multi-block R6 and Multi-block R9 are similar to the polymer of Example5 in Table 2 above.

Base Polymers Table Melt Index (I₂) Copolymer Block Base Polymer Density(g/cc) g/10 min Type Type EO885 0.885 1.5 random NA EO870 0.870 5.0random NA EO875 0.875 3.0 random NA Multi-block R6 0.879 1.09 blockshort Multi-block R9 0.883 0.87 block short Multi-block 0.877 4.7 blocklong R21 Multi-block 0.877 4.6 block short R22 NA = Not Applicable MeltIndex (I₂): 190° C./2.16 kg

Examples Multi-Block R21 and Multi-Block R22 Continuous SolutionPolymerization, Catalyst A1/B2+DEZ

Continuous solution polymerizations were carried out in a computercontrolled, well-mixed reactor. Purified mixed alkanes solvent (Isopar™E available from Exxon Mobil, Inc.), ethylene, 1-octene, and hydrogen(where used) were combined and fed to a 102 L reactor. The feeds to thereactor were measured by mass-flow controllers. The temperature of thefeed stream was controlled by use of a glycol cooled heat exchangerbefore entering the reactor. The catalyst component solutions weremetered using pumps and mass flow meters. The reactor was runliquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive were injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution was then heated in preparation fora two-stage devolatization. The solvent and unreacted monomers wereremoved during the devolatization process. The polymer melt was pumpedto a die for underwater pellet cutting. Process conditions aresummarized in the Process Conditions Table.

Process Conditions for Multi-block R21 and Multi-block R22 Multi-blockR21 Multi-block R22 C₂H₄ (lb/hr)* 55.53 54.83 C₈H₁₆ (lb/hr) 30.97 30.58Solvent (lb/hr) 324.37 326.33 H₂ (sccm¹) 550 60 T (° C.) 120 120 Cat.A1² (ppm) 600 600 Cat. A1 Flow (lb/hr) 0.216 0.217 Cat. B2³ (ppm) 200200 Cat. B2 Flow (lb/hr) 0.609 0.632 DEZ Conc. wt % 3.0 3.0 DEZ Flow(lb/hr) 0.69 1.39 Cocat. 1 Conc. (ppm) 4500 4500 Cocat. 1 Flow (lb/hr)0.61 0.66 Cocat. 2 Conc. (ppm) 525 525 Cocat. 2 Flow (lb/hr) 0.33 0.66[DEZ]⁴ in polymer (ppm) 246 491 Polymerization Rate⁵ 84.13 82.56 (lb/hr)Conversion⁶ (wt %) 88.9 88.1 Polymer (wt %) 17.16 17.07 Efficiency⁷ 293280 *1 lb/hr = 0.45 kg/hr ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl ⁴ppm in final product calculated by mass balance ⁵polymerproduction rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M, where, g M = g Hf + g Z

Melt Maleation Process Example: Melt Maleation—Haake MixerRepresentative Procedure

The base polymer (45.0 grams) was added to a Haake Rheomix 600P mixer,prewarmed to 170° C., and rotating at 10 RPM. The speed of the stirrerwas increased stepwise, over a two minute period, to 60 RPM. Maleicanhydride (MAH, 1.39 grams) was then added to the mixer, and theresultant mixture was mixed for three minutes. Next, a 10 wt % solutionof 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane in dodecane (0.0895grams) was injected into the mixer, and mixing was continued for anadditional 6.25 minutes. The grafted resin, isolated from the mixer, hada MFR of 1.5 (ASTM D-1238, at 190° C./2.16 kg).

The isolated resin was dissolved in hot xylene at a 2-5 wt % percentconcentration. The resin solution was then precipitated in acetone (5×the volume of xylene solution), and the precipitated resin wascollected, washed, and soaked in acetone, and then collected and driedto constant weight.

The dried resin was titrated with 0.02N KOH to determine the amount ofgrafted maleic anhydride. The dried, precipitated polymer was titratedby dissolving 0.3 to 0.5 grams of polymer in about 150 mL of refluxingxylene. Upon complete dissolution, deionized water (four drops) wasadded to the solution, and the solution was refluxed for one hour. Next,1% thymol blue (a few drops) was added to the solution, and the solutionwas over titrated with 0.02N KOH in ethanol, as indicated by theformation of a purple color. The solution was then back-titrated to ayellow endpoint, with 0.05N HCl in isopropanol.

Data summaries for the melt maleation experiments on the baseinterpolymers of melt indexes of approximately one and five are shown inthe Melt Maleation Data Tables.

Melt Maleation Data Table Peroxide MFR Solution Peroxide Radicals* MAHFeed Torque of Final Wt % grams mmol R./100 g MAH Feed grams Nm ProductGrafted T_(m) T_(cr) Polymer (mmoles) (half-lives) Wt % (mmoles) (rpm)g/10 min MAH ° C. ° C. EO885 (as received) — — — — — 1.48 — 85 59 EO885— — — — 36.5 0.54 — — — (Thermally Treated (75)   Only) EO885 — — — —13.2 0.79 — — — (Thermally Treated (60)   Only) EO885 0.0891** 2.5 3.01.39 24.6 0.00 — — — (0.292) (10 half-lives) (14.2) (cured) EO8850.0876** 2.5 5.0 2.37 25.0 0.00 — — — (0.287) (10 half-lives) (24.2)(cured) EO885 0.0907 0.25 3.0 1.39 12.6 0.43 0.23 82 60 (0.0297) (14.2)EO885 0.0892 0.25 5.0 2.37 13.2 0.35 0.29 83 59 (0.0292) (24.2)Multi-block R6 — — — — — 1.09 — 119 93 (as received) Multi-block R6 — —— — 13.0 0.547 — — — (Thermally Treated - 170° C./60 rpm) Multi-block R60.0895 0.25 3.0 1.39 13.2 0.074 0.39 118 91 (0.0293) (14.2) Multi-blockR6 0.0898 0.25 5.0 2.37 13.5 0.043 0.54 117 90 (0.0294) (24.2)Multi-block R9 — — — — — 0.87 — 124 100 (as received) Multi-block R9 — —— — 13.0 0.85 — — — (Thermally Treated - 170° C./60 rpm) Multi-block R90.0880 0.25 3.0 1.39 13.0 0.26 0.39 122 100 (0.0288) (14.2) Multi-blockR9 0.0856 0.25 5.0 2.37 13.8 0.17 0.45 122 100 (0.0280) (24.2)*Theoretical amount of radicals; **Peroxide added as received with nodilution; MRF: 190° C./2.16 kg;; Tm = melting point peak, first heat,10° C./min; Tcr = crystallization temperature, cooling 10° C./min from200° C. Peroxide MFR Solution Peroxide Radicals* MAH Feed of Final Wt %Base grams mmol MAH Feed grams Torque Product Grafted T_(m) T_(cr)Polymer (mmoles) R./100 g Wt % (mmoles) Nm g/10 min MAH ° C. ° C. EO870(as received) — — — — — 4.46 — 53 43 EO870 — — — — 5.2 4.10 — — —(Thermally Treated 170° C. @ 60 rpm) EO870 0.1728 0.50 1.0 0.454 6.11.29 0.59 69 39 (0.0566) (4.63) EO870 0.1625 0.50 3.0 1.39 6.8 0.4770.58 68 40 (0.0533) (14.2) EO870 0.1761 0.50 5.0 2.37 6.5 0.466 0.58 6839 (0.0577) (24.2) EO870 0.0889 0.25 1.0 0.454 6.3 2.07 0.36 67 40(0.0291) (4.63) EO870 0.0889 0.25 3.0 1.39 — 2.38 0.28 69 40 (0.0291)(14.2) EO870 0.0895 0.25 5.0 2.37 5.7 2.35 0.21 69 39 (0.0293) (24.2)EO870 0.0846** 0.125 1.0 0.454 5.0 2.94 — 66 39 (0.0139) (4.63) EO8700.0869** 0.125 3.0 1.39 4.8 2.69 — — 41 (0.0142) (14.2) EO870 0.0869**0.125 5.0 2.37 5.0 2.39 — 68 40 (0.0142) (24.2) *Theoretical amount ofradicals **Peroxide added as 5.0 wt % solution in dodecane Tm = meltingpoint peak, first heat, 10° C./min Tcr = crystallization temperature,cooling 10° C./min from 200° C. MFR: 190° C./2.16 kg Peroxide SolutionMAH Feed Wt % grams Peroxide Radicals* MAH Feed grams Torque MFR GraftedT_(m) T_(cr) Base Polymer (mmoles) mmole R./100 g Wt % (mmoles) Nm g/10min MAH ° C. ° C. Multi-block R21 — — — — — 4.98 — 125 93 (as received)Multi-block R21 — — — — 4.8 4.70 — — — (Thermally Treated - 170° C. @ 60rpm) Multi-block R21 0.1760 0.50 1.0 0.454 5.0 2.26 0.47 122 104(0.0577) (4.63) Multi-block R21 0.1739 0.50 3.0 1.39 6.6 0.512 0.75 122102 (0.0570) (14.2) Multi-block R21 0.1729 0.50 5.0 2.37 7.2 0.304 0.76122 101 (0.0567) (24.2) Multi-block R21 0.0886 0.25 1.0 0.454 4.5 3.100.29 124 103 (0.0290) (4.63) Multi-block R21 0.0895 0.25 3.0 1.39 6.21.46 0.53 123 103 (0.0293) (14.2) Multi-block R21 0.0908 0.25 5.0 2.376.7 1.07 0.57 123 102 (0.0298) (24.2) Multi-block R21 0.0858** 0.125 1.00.454 4.1 4.23 — 125 103 (0.0141) (4.63) Multi-block R21 0.0870** 0.1253.0 1.39 4.8 2.52 — — 104 (0.0143) (14.2) Multi-block R21 0.0872** 0.1255.0 2.37 4.9 1.90 0.33 123 103 (0.0143) (24.2) *Theoretical amount ofradicals **Peroxide added as 5.0 wt % solution in dodecane Tm = meltingpoint peak, first heat, 10° C./min Tcr = crystallization temperature,cooling 10° C./min from 200° C. MFR: 190° C./2.16 kg Peroxide MFRSolution MAH Feed of Final Wt % grams Peroxide Radicals* MAH Feed gramsTorque Product Grafted T_(m) T_(cr) Base Polymer (mmoles) mmole R./100 gWt % (mmoles) Nm g/10 min MAH ° C. ° C. Multi-block R22 — — — — — 4.75 —122 88 (as received) Multi-block R22 — — — — 5.2 4.43 — — — (ThermallyTreated - 170° C. @ 60 rpm) Multi-block R22 0.1686 0.50 1.0 0.454 5.21.68 0.41 120 95 (0.0553) (4.63) Multi-block R22 0.1757 0.50 3.0 1.397.8 0.262 0.75 118 94 (0.0576) (14.2) Multi-block R22 0.1753 0.50 5.02.37 7.2 0.342 0.77 119 94 (0.0575) (24.2) Multi-block R22 0.0895 0.251.0 0.454 4.9 2.78 0.42 120 98 (0.0293) (4.63) Multi-block R22 0.08970.25 3.0 1.39 6.6 1.24 0.54 120 97 (0.0294) (14.2) Multi-block R220.0909 0.25 5.0 2.37 6.7 1.03 0.62 120 95 (0.0298) (24.2) Multi-blockR22 0.0868** 0.125 1.0 0.454 4.5 3.75 — 121 120 (0.0142) (4.63)Multi-block R22 0.0854** 0.125 3.0 1.39 4.6 2.60 — 121 98 (0.0140)(14.2) Multi-block R22 0.0876** 0.125 5.0 2.37 5.1 1.52 0.38 121 97(0.0144) (24.2) *Theoretical amount of radicals **Peroxide added as 5.0wt % solution in dodecane Tm = melting point peak, first heat, 10°C./min Tcr = crystallization temperature, cooling 10° C./min from 200°C. MFR: 190° C./2.16 kg

Example: Melt Maleation—Grafting MAH to Olefin Interpolymer in aTwin-Screw Extruder

MAH-grafted resins were prepared in a continuous reactive extrusionprocess using a twin-screw extruder. The resins used for this processwere EO870, EO875, multi-block R21, and Multi-block R22. The apparatuswas a 30-mm ZSK-30 extruder with a length-to-diameter ratio of 35.67.The temperature set point in the extruder was 235° C. The screw rotationrate was 300 RPM. Resin pellets were fed to the extruder at a rate of 10lb/hr. The peroxide initiator was2,5-bis(t-butylperoxy)-2,5-dimethylhexane. A solution, containingapproximately 1.24 wt % peroxide, 49.38 wt % MAH, and 49.38 wt % methylethyl ketone, was fed into the extruder at a rate of approximately 6.17g/min. This addition rate corresponded to the addition of 4 wt % MAH and1000 ppm peroxide based on the mass of resin. A vacuum port wasinstalled at the end of the extruder to remove methyl ethyl ketone andexcess, ungrafted MAH. The grafted resin exited the extruder and waspelletized and collected.

Approximately 2.5 g of each grafted resin was dissolved in 100 mL ofboiling xylene, and then precipitated by pouring the solution into fivevolumes of acetone. The solids were collected, dried, and titrated todetermine the level of grafted MAH. The EO870 resin contained 1.85 wt %grafted MAH. The EO875 resin contained 1.85 wt % grafted MAH. TheMulti-block R21 resin contained 1.80 wt % grafted MAH. The Multi-blockR22 resin contained 1.49 wt % MAH. The grafted resins were blended witha polyamide resin as discussed in below in the section entitledMAH-grafted Resin/Polyamide Blends.

Solution Maleation Process Example: Solution Maleation—RepresentativeProcedure

The polyolefin (Multi-block resin, EO885 or EO870) (10.0 g) was chargedto a 250-mL flask. Next, maleic anhydride (0.5 g) and anhydrous xylene(100 mL) were added. The mixture was stirred and heated to reflux todissolve the polymer and the maleic anhydride, and then the temperatureof the solution was decreased to 120° C. Next, a solution containing0.03 g of benzoyl peroxide (equivalent to 2.5 mmol benzoyloxy radicalsper 100 g polymer) in xylene was added to the solution. The mixture wasallowed to react for 30 minutes at 120° C. (approximately 10half-lives), and then the temperature was increased to reflux. Thesolution was refluxed for one hour to fully decompose the peroxide. Thegrafted product was isolated by pouring the reaction mixture into 500 mLof acetone, collecting the solid by filtration, and drying the solid.The solid was then dissolved in boiling xylene, precipitated into fivevolumes acetone, and dried. The grafted product was analyzed asdescribed above. The summary of the data is shown in Solution MaleationTables below.

Solution Maleation Data Table Multi- Multi- Multi- block Multi- blockEO885 EO885 block R6 R6 block R9 R9 (as (MAH (as (MAH (as (MAH received)grafted) received) grafted) received) grafted) MFR of 1.48 0.26 1.090.12 0.87 0.21 Resin (g/10 min) Grafted NA 0.45 NA 0.49 NA 0.35 MAH (wt%) NA = Not Applicable MFR measured at 190° C./2.16 kg

Solution Maleation Data Table Multi- Multi- Multi- block Multi- blockEO870 EO870 block R21 R21 block R22 R22 (as (MAH (as (MAH (as (MAHreceived) grafted) received) grafted) received) grafted) MFR of 4.462.57 4.98 2.26 4.75 1.99 Resin (g/10 min) Grafted NA 0.46 NA 0.37 NA0.34 MAH (wt %) NA = Not Applicable MFR measured at 190° C./2.16 kg

Melt Maleation by Imbibing Process Example: Melt Maleation by ImbibingProcess—Representative Procedure

Maleic anhydride (1.46 g) and toluene (7.7 mL) were added to a 250-mL,one neck, round bottom flask. The mixture was warmed slightly to effectdissolution. Next, a 10 wt % solution of2,5-dimethyl-2,5-di(tert-butylperoxy)hexane in dodecane (0.0933 g) wasinjected into the flask, and 45.0 grams of the polyolefin (Multi-blockR21, Multi-block R22, or EO870) was added to the flask. The flask wasthen rotated for an overnight period, at room temperature, and itscontents were then air-dried. The air-dried product was then transferredto a Haake Rheomix 600P mixer, prewarmed at 170° C., and rotating at 10RPM. The rotation speed was increased stepwise to 60 RPM over a twominute period. The contents of the mixer were mixed for 9.25 minutes,and then analyzed as described above. The data is summarized in ImbibingMaleation Data Table.

Imbibing Maleation Data Table Peroxide Peroxide Solution Radicals* MAHMAH Feed Wt % grams mmole Feed grams Torque MFR Grafted T_(m) T_(cr)Resin (mmoles) R./100 g Wt % (mmole) Nm g/10 min MAH ° C. ° C. EO8700.0933 0.27 3.1 1.46 5.5 3.52 — 68 40 (0.0306) (14.9) Multi-block 0.09330.27 3.1 1.46 5.3 4.10 — 121 105 R21 (0.0306) (14.9) Multi-block 0.09330.27 3.1 1.46 5.6 3.47 — 121 99 R22 (0.0306) (14.9) Multi-block 0.18660.54 3.1 1.46 5.8 1.46 0.51 123 101 R21 (0.0612) (14.9) *Theoreticalamount of radicals T_(m) = melting point peak, first heat, 10° C./minT_(cr) = crystallization temperature, cooling 10° C./min, from 200° C.MFR measured at 190° C./2.16 kg

Solid State Maleation Example: Solid State Maleation—Multi-block R21

Maleic anhydride (1.46 grams, 14.9 mmoles) and toluene (7.7 mL) wereadded to a 1-neck, 250 mL round bottom flask, and the contents of theflask were warmed slightly to effect dissolution. Next, a solutioncontaining 7.4 wt % of benzoyl peroxide in toluene (1.91 grams, 0.584mmol) was injected into the flask, and the Multi-block R21 (45.0 grams)was added to the flask. The contents in the flask were rotated overnightat room temperature, and then air-dried. The air-dried product wasreloaded into a 1-neck, 250 mL round bottom flask, and deoxygenated. Theproduct was kept under nitrogen, and agitated, while warmed at 90° C.for 8 hours.

A three gram aliquot of product was brought to a boil in ˜135 mL boilingxylenes, and the soluble fraction was precipitated in ˜600 mL of stirredacetone. The precipitated product was collected by filtration, washedand soaked in fresh acetone, recollected, and dried to constant weightat approximately 55° C. in a vacuum oven. FTIR analysis of a pressedfilm of the precipitated polymer showed the characteristic carbonyls ofgrafted maleic anhydride/succinic anhydride (and hydrolyzed forms) at˜1711 cm⁻¹, 1789 cm⁻¹, and ˜1865 cm⁻¹. By titration, the weight % ofgrafted maleic anhydride was 0.47%. The product had a melting point of122° C., determined by DSC, at a 10° C./min heating rate. The producthad a crystallization temperature of 100° C., determined by DSC, at a10° C./min cooling rate, from 200° C.

Example: Solid State Maleation—Multi-block R21

Maleic anhydride (1.46 grams, 14.9 mmoles) and toluene (7.7 mL) wereadded to a 1-neck, 250 mL round bottom flask. The contents were warmedslightly to effect dissolution. A solution containing 7.4 wt % ofbenzoyl peroxide in toluene (0.38 grams, 0.116 mmol) was injected intothe flask, and Multi-block R21 (45.0 grams) was added to the flask. Thecontents of the flask were rotated overnight at room temperature. Theflask was deoxygenated, kept under nitrogen, and contents agitated,while warmed at 90° C. for 8 hours. Melt flow rates (MFR) were performedaccording to ASTM D-1238 at 190° C. and 2.16 kg. The isolated crudeproduct had a MFR of 1.8 g/10 min.

A three gram aliquot of product was brought to a boil in approximately135 mL boiling xylenes, and then and precipitated in ˜600 mL of stirredacetone. The precipitated product was collected by filtration, washedand soaked in fresh acetone, recollected, and dried to constant weightat approximately 55° C. in a vacuum oven. FTIR of a pressed film of theprecipitated polymer showed characteristic carbonyls of grafted maleicanhydride/succinic hydride (and hydrolyzed forms) ˜1788 cm⁻¹, and 1865cm⁻¹. By titration, the weight % of grafted maleic anhydride was 0.21%.Melting point=124° C. at 10° C./min heating rate. Crystallizationtemperature=102° C., at 10° C./min cooling from 200° C.

MAH-Grafted Resin/Polyamide Blends MAH-Grafted Resins

Melt index data on MAH-grafted resins are shown below in GPC and MeltIndex Data Table.

GPC and Melt Index Data Wt % grafted I₂ Resin MAH g/10 min 1.MAH-g-EO870* 1.85 0.0912 2. MAH-g-EO875* 1.85 0.049 3. MAH-g-Multi-blockR22 1.49 0.2393 4. MAH-g-Multi-block R21 1.80 0.1482 *Comparative resinsI₂: 190 C/2.16 kg

Blends: Representative Procedure

Approximately 454 grams of the maleic anhydride grafted resin(MAH-g-EO870, MAH-g-875, MAH-g-Multi-block R22 or the MAH-g-Multi-blockR21) was pellet blended with 1816 grams of a polyamide (Ultramide® B-3,available from BASF), by feeding both resins into a 25 mm Haake twinscrew extruder at an instantaneous rate of 2724 grams per hour. Theextruder temperature profile was a constant 250° C. The collected samplewas subsequently injection molded to produce ASTM test bars for IZOD andflexural modulus testing. Mechanical Test data is summarized inMechanical Data Table below.

Mechanical Data Table Avg. Avg. Avg. Secant Avg.Izod- Flex. Flex. Mod.RT @ B- Avg. Color of Strength Mod. @ 1% 3833 Izod molded Resin psi ksiksi ft-lbs/in J/m plaques 1. MAH-g-EO870 5873 267 266 7.391 394.6 tan 2.MAH-g-EO875 5799 265 265 10.08 537.9 tan 3. MAH-g-Multi- 5864 264 2648.624 460.4 tan blockR22 4. MAH-g-Multi- 5463 246 246 7.346 392.2 tanblockR21

The lower viscosity Multi-block resins have comparable or even bettermechanical properties, compared to the higher viscosity comparativeresins.

The resins were made into injection molded plaques and tested for impactproperties. The results are shown in the table below.

Impact Average Impact Tester Izod Avg Flexural Tester (Room Impact ResinModulus (ksi) (30° C.) Temp) (J/m) 1. MAH-g-EO870 267 with standard48.62 56.99 394.6 deviation of 6 2. MAH-g-EO875 265 with standard 58.1856.64 537.9 deviation of 4 3. MAH-g-Multi- 264 with standard 68.17 63.25460.4 blockR22 deviation of 10 4. MAH-g-Multi- 246 with standard 63.9266.25 392.2 blockR21 deviation of 9

Note: the Inventive polymers (Run #3 & 4) have significantly higherimpact resistance at low temperature vs. the comparative samples (Run #1& 2). Sample #3 has the best balance between high modulus and highimpact. This improved impact is demonstrated at both room temperatureand at low temperature. The test pieces were injection molded plaquesand the test was completed using the procedure as outlined in ASTM D3763 (Injection Molded Parts). Flex modulus was done according to ASTMD-790 and Izod impact was done according to D-256.

Grafting ¹³C-Labelled Maleic Anhydride Representative Procedure

A 50-mL 3-neck flask was charged with 2.0 g of polyolefin resin (EO870,Multi-block R21, or Multi-block R22), 0.1 g of 2,3-¹³C₂-maleicanhydride, and 20 mL of anhydrous xylene. This mixture was stirred andheated to reflux to dissolve the polymer and MAH, and then thetemperature was decreased to 120° C. A solution containing 0.006 g ofbenzoyl peroxide in xylene was added; this is equivalent to 2.5 mmolesof benzoyloxy radicals per 100 g of polymer. After allowing the mixtureto react at 120° C. for 30 minutes, approximately 10 half-lives, thetemperature was increased to reflux for one hour in order to fullydecompose the peroxide. The product was isolated by pouring the reactionmixture into 100 mL of acetone and filtering the precipitate. Thecollected solid was dissolved in boiling xylene, precipitated into fivevolumes of acetone, and dried. The products and base resins wereanalyzed by ¹³C NMR spectroscopy.

NMR was used to determine the ethylene-to-octene (E/O) mole ratio of thebase resins. The results are as follows:

EO870:E/O=87.5:12.5;

Multi-block R21:E/O=88.1:11.9;

Multi-block R22:E/O=88.2:11.8.

The ratio of “CH₂ groups to CH groups (or CH₂/CH)” in each of the baseresins is as follows:

EO870:CH₂/CH=20.3;

Multi-block R21:CH₂/CH=20.7;

Multi-block R22:CH₂/CH=19.4.

This ratio was based in the number of “CH” and “CH₂” groups in thesample (one CH group and six CH₂ groups for each octene, and two CH₂groups for each ethylene).

NMR was used to determine the location of the graft site of the¹³C-labelled MAH, whether at a CH₂ site or a CH site. The results are asfollows:

EO870:CH₂-graft/CH-graft=4.4;

Multi-block R21:CH₂-graft/CH-graft=6.2;

Multi-block R22:CH₂-graft/CH-graft=4.9.

Since the ratios of CH₂-graft/CH-graft in the grafted resins areconsiderably smaller than the corresponding ratios of CH₂/CH sites inthe base resins, this indicates that, relative to the total number ofeach available site, there is a preference for grafting at a CH site.This is reflected in the lower dissociation energy of the tertiary C—Hbond compared to that of the secondary C—H bond, and the faster rate ofhydrogen abstraction from a tertiary CH compared to the rate of hydrogenabstraction from a secondary CH₂ (see: G.-H. Hu, J.-J. Flat, M. Lambla,in S. Al-Malaika, ed., “Reactive Modifiers for Polymers,” BlackieAcademic & Professional, London, 1997, p. 11; K. E. Russell, Prog.Polym. Sci. 27 (2002), 1007).

Silanation of Olefin Interpolymers Description of Base Polymers

The base interpolymers are described in Base Polymers Table above.

Grafting of Vinyltriethoxysilane onto EO870 and Multi-Block R21 andMulti-Block R22

Representative Procedure

A glass jar was loaded with vinyltriethoxysilane (VTES, 1.81 g, 9.51mmol), 10 wt % of LUPEROXT™101 in VTES (0.18 g, 0.059 mmol), and polymer(EO870, Multi-block R21 or Multi-block R22) (50.00 grams). The jar wassealed and thermally treated overnight at approximately 40° C. Theimbibed polymer was added to a Haake Rheomix 600P, prewarmed to 190° C.,and rotating at 10 RPM. The speed of rotation was increased stepwiseover 2 minutes to 60 RPM. Mixing was continued for 2.7 minutes, and thena sample (˜7 grams) was removed for infrared analysis and melt flow ratemeasurement. Dibutyltin dilaurate (DBTDL, 0.09 grams, 0.14 mmol) wasthen added, and the mixing was continued for another 5 minutes. Theproduct was then removed and cooled to room temperature.

Melt flow rates (MFR) were performed according to ASTM D-1238 at 190° C.and 2.16 kg. For the EO870 grafted sample, the MFR was 3.0 g/10 minutes;for the Multi-block R21 grafted sample, the MFR was 3.9 g/10 minutes;and for the Multi-block R22 grafted sample, the MFR was 3.1 g/10minutes.

Determining Levels of Grafted Silane

A small portion of each grafted product that did not contain dibutyltindilaurate was compression molded at 150° C. to a film, and each film wasplaced in a vacuum oven at 65° C., overnight, to remove residual VTESthat was not grafted. Then, the infrared spectrum of each was collected(FIGS. 10 and 11).

The FTIR spectra were used for determining the level of grafted VTES ineach sample. Using a method that has been calibrated against neutronactivation analysis, the wt % of grafted VTES was determined from theratio of the height of the peak at 1105 cm⁻¹, corresponding to theabsorption of the Si—O—C group, to the height of the C—H peak at 2017cm⁻¹, as follows:

${{wt}\mspace{14mu} \% \mspace{14mu} {VTES}} = {{0.1156\left( \frac{{peak}\mspace{14mu} {{ht}@1105}\mspace{14mu} {cm}^{- 1}}{{peak}\mspace{14mu} {{ht}@2017}\mspace{14mu} {cm}^{- 1}} \right)} + {0.0345.}}$

The FTIR results are shown below.

FTIR Results Base Resin Grafted VTES Content EO870 3.59 wt % Multi-blockR21 3.53 wt % Multi-block R22 3.50 wt %

Crosslinking the Silane-Grafted Resins

Approximately 6.5 g of the portion of each grafted product thatcontained dibutyltin dilaurate was compression molded at 150° C., usinga stainless steel mold, to a plaque that was approximately 4″ by 4″ by0.030″ in size. Each plaque was immersed in water, inside a sealed glassjar, and the jar was placed in an oven equilibrated at 90° C., andthermally treated for 7 days. After this time, the crosslinked plaqueswere removed from the water, rinsed with fresh water, and dried in avacuum oven overnight at 65° C.

Approximately 2 g of each crosslinked product was cut into thin stripsand placed in a weighed glass fiber extraction thimble, and the exactweight was determined. The thimble was pinched closed and stapled, andthe exact weight was determined again. The sealed thimble was placed ina Soxhlet extractor, and the samples were extracted with boiling xylenes(bp 138-141° C.) for 24 hours. The thimble was removed from theextractor and dried in a vacuum oven at 65° C. overnight. The exactweight of the dried thimble and sample residue was determined, and thegel fraction, which is the weight fraction that was not soluble inxylene, was calculated. The extraction results for the samples are shownin the Extraction Data Table below. As shown from the data, the graftedresins were substantially crosslinked.

Extraction Data Table Multi-block Multi-block Base Resin EO870 R21 R22Sample wt. before 2.2170 g 2.1285 g 2.3494 g extraction Sample residuewt. 1.8849 g 1.8232 g 2.0229 g after extraction Gel Fraction 85.0% 85.7%86.1%

Silane Grafting of High Melt Flow Polyolefins Using Reactive ExtrusionBase Ethylene/α-Olefin Interpolymer Preparation

Continuous solution polymerizations were carried out in a computercontrolled well-mixed reactor equipped with an internal stirrer.Purified mixed alkanes solvent (ISOPAR™ E available from ExxonMobil,Inc.), ethylene at 5.96 lbs/hour (2.7 kg/hour), 1-octene, and hydrogen(where used) were supplied to a 5.0 L reactor equipped with a jacket fortemperature control and an internal thermocouple. The solvent fed to thereactor was measured by a mass-flow controller. A variable speeddiaphragm pump controlled the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream was taken toprovide flush flows for the catalyst and cocatalyst 1 injection linesand the reactor agitator. These flows were measured by Micro-Motion massflow meters and controlled by control valves or by the manual adjustmentof needle valves. The remaining solvent was combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller was used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution was controlled by using aheat exchanger before entering the reactor. This stream entered thebottom of the reactor. The catalyst component solutions were meteredusing pumps and mass flow meters and were combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactorwas run liquid-full at 406 psig (2.8 MPa) with vigorous stirring.Product was removed through exit lines at the top of the reactor. Allexit lines from the reactor were steam traced and insulated.Polymerization was stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream was thenheated up through heat exchangers, and passes two devolatizers in seriesbefore it was water cooled Process and product details and results arecontained in the following tables.

Other properties methods have been described previously. Melt viscosityis determined by ASTM D3236, which is incorporated herein by reference,using a Brookfield Laboratories DVII+ Viscometer equipped withdisposable aluminum sample chambers. In general, a SC-31 spindle isused, suitable for measuring viscosities in the range of from 30 to100,000 centipoise (cP). If the viscosity is outside this range, analternate spindle should be used which is suitable for the viscosity ofthe polymer. A cutting blade is employed to cut samples into piecessmall enough to fit into the 1 inch wide, 5 inches long samples chamber.The disposable tube is charged with 8-9 grams of polymer. The sample isplaced in the chamber, which is in turn inserted into a BrookfieldThermosel and locked into place with bent needle-nose pliers. The samplechamber has a notch on the bottom that fits in the bottom of theBrookfield Thermosel to ensure that the chamber is not allowed to turnwhen the spindle is inserted and spinning. The sample is heated to thedesired temperature (177° C./350° F.). The viscometer apparatus islowered and the spindle submerged into the sample chamber. Lowering iscontinued until brackets on the viscometer align on the Thermosel. Theviscometer is turned on, and set to a shear rate which leads to a torquereading in the range of 40 to 70 percent. Readings are taken everyminute for about 15 minutes, or until the values stabilize, and then thefinal reading is recorded. The Brookfield viscosity test results arelisted in the following table.

TABLE Process Conditions and Results for Multi-Block 500. Cat A1 Cat B2C₂H₄ C₈H₁₆ Solv. H₂ Temp Cat A1² Flow Cat B2³ Flow DEZ Example kg/hrkg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm kg/hr Conc. % Multi- 2.7 3.6 21.0200 121 150 0.094 76.6 0.049 1.0 Block 500⁸ Zn⁴ DEZ Cocat 1 Cocat 1Cocat 2 Cocat 2 in Poly Flow Conc. Flow Conc. Flow polymer Rate⁵ Conv.Example kg/hr ppm kg/hr ppm kg/hr ppm kg/hr %⁶ Solids % Eff.⁷ Multi- 0.31008 0.16 0 0 750 4.0 90.0 16.0 232 Block 500⁸ ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴ppm in final product calculated by mass balance⁵polymer production rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z ⁸Additive package:1200 ppm Irganox 1010.

TABLE The Properties of Multi-Block 500 and AFFINITY ® GA 1950.Brookfield Heat of Tensile Density Viscosity@ 177° C. M_(w) M_(n) FusionT_(m) T_(m2) T_(c) T_(c2) Strength Elongation at Sample (g/cm³) (cP)(g/mol) (g/mol) M_(w)/M_(n) (J/g) (° C.) (° C.) (° C.) (° C.) (MPa)Break (%) Multi-block 0.8771 15,757 22,400 9,720 2.3 60 110 96 95 20.32.1 190 500 AFFINITY ® 0.8755 15,237 22,500 10,100 2.2 64 72 NA 53 332.3 262 GA 1950¹ NM: Not Measured NA: Not Applicable ¹AFFINITY ® GA 1950is a polyolefin plastomer obtained from The Dow Chemical Co., Midland,MI.

For the neutron activation measurements, duplicate samples were preparedby transferring approximately 3.5 g of the polymer into pre-cleaned2-dram polyethylene vials. Duplicate standard samples of Si wereprepared from its standard solution into similar vials. The standardswere diluted using pure water. The samples and the standards were thenanalyzed following the standard NAA procedure (ASIA-SOP-G.005) for Si.Notice that the samples were transferred to un-irradiated vials beforeperforming the gamma spectroscopy. The Si measured in ppm was thenconverted to wt % Si and then wt % VTMS by: (wt % Si)×5.277=wt % VTMS.

Silane Grafting the High Flow Polymers

AFFINITY® GA1950 and a polymer of this invention with similar viscosityand overall density, Multi-block 500, with properties discussed above,were silane grafted according to the following representative procedure.The VTMS silane A-171 by General Electric was added at 4 wt % andTrigonox 101 peroxide by Akzo Noble was added at 950 and 1050 ppm. Theresin and the silane/peroxide were combined together and the liquidmasterbatch was fed into the extruder into the solids feed zone beforemelting section. Both the copolymers were stabilized with Irganox™ 1010,available from Ciba Specialty Chemicals, before the melting section.

The copolymer feedstock and a liquid silane/peroxide masterbatch mixturecontaining vinyltrimethoxysilane (VTMS, 0.87 lb (0.395 kg)) andTrignox®101 (2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, 4.1 g) weresimultaneously added to the feed throat of a co-rotating twin screw,continuous extruder (Werner & Pfleiderer-ZSK 30, with an eleven barrelsection extruder). Each barrel section was 90 mm in length, and thebarrel sections were stacked length-to-length. The temperatures for theinternal barrel sections 3-9 were set at 220° C.-240° C. Barrel sections1, 2, 10 and 11 were not heated, but the temperatures of barrel sections10 and 11 did increase via heat transfer from the molten resin. Thetotal throughput was 10 lb/hr (4.54 kg/hr), and the extruder operated at300 RPM. The residence time of the resin through the extruder was around1-4 minutes. The mixture was continuously extruded though a die plate,quenched in an underwater pelletizer, and cut into pellets. The pelletwater temperature was maintained below 23° C. to ease pelletizing and toprevent pellet agglomerates. During the extrusion, a portion of theunreacted silane was removed from the extruder through a vacuum vent setat −25 inches Hg (−635 mm Hg) located at barrel section 9, locatedtowards the end of the extruder.

The weight percentage of silane within the extrudate was determined fromthe mass flow of the resin, and the volumetric flow rate of thesilane/peroxide masterbatch, which was converted to mass flow rate basedon a calibration.

A screw design that provides a longer residence time and proper melttemperature profile characteristics improves the grafting efficiency.The length and the length-to-diameter ratio (L/D) of the screw designhas been shown to provide little effect on the grafting efficiency.However, the screw design can have an effect on the optimum graftingefficiency of the process. The melt temperatures of 220° C. gaveslightly higher silane graft level for the same amount of VTMS silaneadded than the temperature of 240° C. Also, the type of silane used forgrafting can have an effect on the grafting efficiency with otherparameters being the same. For example, the grafting efficiency withVTMS is lower at the higher temperatures, while with VTES it is higher.Two comparative screws (#Si-g-EO-4 screw design and #HMA Si-g-EO-1 screwdesign), having the same overall length and length-to-diameter ratio(L/D), produced different levels of grafted polymer. However, one screwdesign, the Si-g EO-4 design, had a longer melt residence time than theother screw design, the HMA Si-g-EO-1 design. The Si-g-EO-4 screw designhad a melting zone that started at 6 L/D from the feed end of the screwto the end of the extruder, while the HMA Si-g-EO -1 screw design hadthe same, but in addition it utilized a greater number of kneadingblocks, throughout the length of the screw, and these kneading blockswere designed for more intensive kneading and provide a longer residencetime, especially in the mixing and melting zones. Thus, the earliermelting of the materials within the extruder and the higher extrusiontemperature peak, coupled with a longer material residence time, wereadvantageous for achieving an increased level of silane grafting.

The following table provides a summary of the weight percentages ofsilane added into the extruder, and the % VTMS in the extrudate. Theweight of the silane and peroxide are each based on the total weight ofthe reactive composition (base resin (or resin formulation) plus silaneplus peroxide).

As seen from the table, the % VTMS in the extrudate was good for thesamples produced from an extruder equipped with the HMA Si-g-EO-1 screwdesign. For the same level of peroxide and silane added, Multi-block 500block gave a higher level of grafting than the AFFINITY® GA1950 randomethylene/octene copolymer.

TABLE Summary of VTMS Grafting Results. Peroxide, Silane Feed ScrewBARREL #6 MELT added to added to % VTMS Rate, Speed, THERMOCOUPLEextruder extruder, Neutron Material: lb/hr rpm (° C.) ppm wt %Activation* AFFINITY ® GA 1950 10 300 237 1050 4 2.13 Multi-Block 500 10300 238 1050 4 2.53 *Measured on pellets (not dried in vacuum oven)

Curing of Silane Grafted Resins and Resulting Properties

The silane grafted AFFINITY® GA 1950 previously described and the silanegrafted Multi-Block 500 previously described were silane cured asfollows, resulting in silane grafted and cured products, si-AFFINITY® GA1950 and si-Multi-Block 500. The Haake bowl temperature was set at 100°C. The Rheomix 600 (50 gram) bowl was preheated to 100° C. The rotorswere started at 30 rpm. The sealed foil bag containing the silanegrafted polymer was opened to remove 50 grams which was immediatelyadded to the bowl. After 2 minutes of rotation and melting, the ram waslifted, and 0.1 g (2000 ppm) of ALDRICH 95% Di-butyl tin dilaurate wasadded. The ram was lowered to continue mixing. The blend was allowed tomix for an additional 6 minutes. The polymer was then removed andpressed in Mylar in a room temperature press to solidify the sample. Thepolymer was then molded into 1-80 mil×5″×5″ plaques on a laminatingpress. The plaque was then placed in a tray of water which had beenplaced in an oven heated to 45° C. for 114 hours. The plaques were driedand then tested.

Results include the density, the % gel from xylene extractables, the %VTMS from neutron activation (as described previously), the thermalproperties from DSC, mechanical properties from tensile data, and solidstate dynamic mechanical data (these were measured as previously but at1 rad/s). These procedures have been reported previously; the % gel fromxylene extractables and the mechanical properties tests will bedescribed here.

The xylene extractables are the portion of the polymer soluble inrefluxing xylene after 12 hours. It is measured as the percentage ofweight loss of the sample. The test is run according to ASTM D2765. Thenon-extractable portion is referred to as the gel content and isreported in %. These properties were measured on the base polymer andthe silane grafted and cured polymer. The mechanical properties weremeasured on an Instron Model 5564. The samples were approximately 1.85mm thick and were pulled at 5″/min. The microtensile specimens conformedto ASTM D-1708.

The results are reported in the following table.

TABLE Properties of AFFINITY ® GA 1950 and Multiblock 500 and the silanegrafted and cured properties (si-AFFINITY ® GA 1950 and si-Muliblock500). % % Gel Cryst % from Heat of Based Density Xylene Xylene T_(m1)T_(m2) Fusion on T_(c1) T_(c2) T_(c3) T_(g) (g/cc) ExtractablesExtractables (° C.) (° C.) (J/g) 292 J/g (° C.) (° C.) (° C.) (° C.)AFFINITY ® GA 1950 0.8801 72 56 53 18 54 34 −52 Multiblock 500 0.8806114 97 43 15 101 90 19 −61 si-AFFINITY ® 0.8796 36 64 71 51 18 53 −51GA1950¹ si-Multiblock 500¹ 0.8801 31 69 100 40 14 100 75 −56 EnergyYield Stress % Elongation at Young's 2% Secant Modulus at Max. LoadTensile Strength (Psi) Break Modulus (Psi) (Psi) (in-lbf) (Psi)AFFINITY ® 293 123 1292 813 4 306 GA 1950 Multiblock 500 266 105 1219156 3 279 si-AFFINITY ® 467 253 2028 1501 13 659 GA1950¹ si-Multiblock335 257 4222 3108 14 745 500¹ ¹Silane grafted and cured.

As shown above and previously, AFFINITY® GA 1950 and Multi-block 500 hadcomparable density and Brookfield viscosity. At equivalent graftingprocess conditions, Multi-block 500 showed a more favorableincorporation of VTMS (2.53%) as compared to AFFINITY® GA 1950 (2.13%)indicating a more efficient incorporation of silane resulting in morebeneficial process economics. Higher melting temperatures (T_(m1) andT_(m2), T_(m1) representing the primary melting temperature and T_(m)2representing a secondary more minor melting temperature) are seen forMulti-block 500 (T_(m1) of 114° C.) and si-Multi-block 500 (T_(m1) of100° C.) as compared to AFFINITY® GA 1950 (T_(m1) of 72° C.) andsi-AFFINITY® GA 1950 (T_(m1) of 71° C.) as shown in the attached FIG.12. Multi-block 500 also shows lower glass transition temperatures(T_(g)) than AFFINITY® GA 1950 indicating better low temperatureproperties. The mechanical properties of the silane grafted and curedsi-Multi-block 500 shows excellent elongation, Young's modulus, 2%Secant modulus, and tensile strength as compared to the si-AFFINITY® GA1950. The mechanical properties in the previous table are the average of5 replicates. A representative comparison is shown in the attached FIG.13. The solid state dynamical mechanical properties are shown in theattached FIG. 14 and show for the si-Multi-block 500 that the storagemodulus shows a high and stable value at elevated temperature greaterthan 100° C. indicating good high temperature resistance. This is incontrast to the si-AFFINITY® GA1950 where the modulus is low at hightemperature, indicating poor low temperature resistance. A dramaticchange in the high temperature properties is also seen when Multi-block500 and si-Multi-block 500 are compared, showing the effectiveness ofthe silanation and curing. The tan delta, or ratio of loss to storagemodulus (G″/G″) is shown in the attached FIG. 15. Again, glasstransition temperatures are lower for Multi-block 500 and si-Multi-block500 as compared to AFFINITY® GA 1950 and si-AFFINITY® GA 1950. This isinferred from the peak at low temperatures. Additionally at highertemperatures the tan delta of si-Multi-block 500 remains low, indicatinggood elasticity at high temperatures. These data are summarized in theattached table. Multi-block 500 with its low viscosity and good hightemperature properties is expected to show good properties as anadhesive when especially when mixed with a tackifier and oil and cured.

TABLE Solid state dynamic mechanical G′ and tan delta on AFFINITY ®GA-1950, Multi- block 500, si-AFFINITY ® GA-1950, and si-Multi-block500. Tan Delta G′ (Pa) Tan Delta G′ (Pa) Tan Delta G′ (Pa) si- si- G′(Pa) si- Tan Delta AFFINITY ® AFFINITY ® Multi- Multi- AFFINITY ®AFFINITY ® Multi- si-Multi- Temp (° C.) GA1950 GA1950 block 500 block500 GA1950 GA1950 block 500 block 500 −100 1.50E+09 −0.0043 1.70E+09−0.0052 1.42E+09 0.0161 1.46E+09 0.0153 −95 1.49E+09 0.0024 1.64E+09−0.0029 1.40E+09 0.0161 1.42E+09 0.0183 −90 1.43E+09 0.0074 1.58E+09−0.0010 1.35E+09 0.0204 1.37E+09 0.0235 −85 1.38E+09 0.0147 1.52E+090.0027 1.30E+09 0.0261 1.31E+09 0.0318 −80 1.33E+09 0.0229 1.44E+090.0092 1.25E+09 0.0336 1.26E+09 0.0410 −75 1.27E+09 0.0319 1.35E+090.0265 1.19E+09 0.0419 1.20E+09 0.0508 −70 1.20E+09 0.0449 1.24E+090.0477 1.12E+09 0.0528 1.12E+09 0.0641 −65 1.10E+09 0.0641 1.13E+090.0795 1.04E+09 0.0715 1.02E+09 0.0866 −60 9.59E+08 0.0951 8.98E+080.1402 9.05E+08 0.1061 8.63E+08 0.1329 −55 7.41E+08 0.1483 5.84E+080.2149 7.03E+08 0.1674 6.30E+08 0.2120 −50 4.89E+08 0.2157 3.47E+080.2469 4.64E+08 0.2471 3.98E+08 0.2682 −45 2.95E+08 0.2522 2.14E+080.2191 2.65E+08 0.3079 2.43E+08 0.2697 −40 1.82E+08 0.2416 1.47E+080.1711 1.56E+08 0.2915 1.61E+08 0.2232 −35 1.18E+08 0.2166 1.09E+080.1401 9.97E+07 0.2460 1.19E+08 0.1713 −30 8.31E+07 0.1904 8.57E+070.1283 6.81E+07 0.1997 9.49E+07 0.1377 −25 5.96E+07 0.1768 6.89E+070.1240 5.07E+07 0.1635 7.95E+07 0.1125 −20 4.60E+07 0.1704 5.69E+070.1271 3.92E+07 0.1401 6.76E+07 0.1117 −15 3.72E+07 0.1564 4.81E+070.1177 3.20E+07 0.1245 5.87E+07 0.1063 −10 3.01E+07 0.1500 4.05E+070.1295 2.65E+07 0.1117 5.15E+07 0.1058 −5 2.49E+07 0.1326 3.46E+070.1268 2.26E+07 0.1042 4.47E+07 0.1222 0 2.13E+07 0.1237 2.96E+07 0.12881.95E+07 0.0925 3.94E+07 0.1268 5 1.81E+07 0.1141 2.50E+07 0.15011.69E+07 0.0869 3.47E+07 0.1344 10 1.56E+07 0.1091 2.11E+07 0.15371.46E+07 0.0860 2.95E+07 0.1589 15 1.31E+07 0.1054 1.77E+07 0.17151.23E+07 0.0810 2.56E+07 0.1678 20 1.12E+07 0.1023 1.50E+07 0.17461.04E+07 0.0772 2.20E+07 0.1807 26 7.45E+06 0.1214 1.16E+07 0.18507.17E+06 0.0877 1.59E+07 0.2036 30 6.68E+06 0.1244 1.02E+07 0.18886.47E+06 0.0892 1.40E+07 0.2276 35 5.33E+06 0.1357 8.30E+06 0.19555.13E+06 0.0958 1.25E+07 0.2291 40 3.58E+06 0.1564 6.44E+06 0.20943.63E+06 0.0991 1.12E+07 0.2323 45 2.55E+06 0.1660 4.99E+06 0.21492.83E+06 0.1012 1.00E+07 0.2355 50 1.85E+06 0.1799 3.70E+06 0.23062.37E+06 0.1113 8.72E+06 0.2478 55 1.35E+06 0.1928 2.80E+06 0.22642.01E+06 0.1230 7.89E+06 0.2433 60 9.32E+05 0.2132 2.00E+06 0.22411.63E+06 0.1425 7.04E+06 0.2389 65 5.25E+05 0.2383 1.35E+06 0.21311.14E+06 0.1861 5.90E+06 0.2383 70 2.13E+05 0.2900 9.15E+05 0.20385.82E+05 0.2297 4.38E+06 0.2372 75 48231 0.4426 5.63E+05 0.2002 2.11E+050.2435 3.41E+06 0.2284 80 4357.61 1.3004 3.10E+05 0.2016 75128.2 0.34682.73E+06 0.2155 85 249.978 8.8342 1.36E+05 0.2298 34498.2 0.53152.19E+06 0.2007 90 −337.85 0.6853 39387.1 0.3147 26323.3 0.5652 1.73E+060.1857 95 382.492 −1.3694 6014.76 0.8614 24373.6 0.5391 1.31E+06 0.1679100 182.324 11.8690 24051.8 0.4831 9.54E+05 0.1478 105 26170.1 0.41016.63E+05 0.1190 110 30495.2 0.3244 4.42E+05 0.0848 115 36501.1 0.26373.01E+05 0.0452 120 43352.1 0.1913 2.66E+05 0.0323 125 48313.8 0.17592.78E+05 0.0304 130 52862.6 0.1330 2.98E+05 0.0295 135 42034.9 0.15553.20E+05 0.0230 140 29167.4 0.2329 3.37E+05 0.0258 145 18065.4 0.30693.56E+05 0.0229 150 9804.16 0.6027 3.68E+05 0.0251 155 7524.3 0.71633.77E+05 0.0205 160 −1148.7 −4.7266 3.89E+05 0.0228 165 −7487.9 −0.70244.00E+05 0.0244 170 −20760 −0.1633 4.15E+05 0.0228 175 4.28E+05 0.0229180 4.43E+05 0.0210 185 4.55E+05 0.0220 190 4.68E+05 0.0220 195 4.79E+050.0202 200 4.89E+05 0.0219Modification of Base Polymer with BSA or Peroxide

A series of polymer samples was prepared on a twin screw extruder inwhich the polymer was modified through the use of various levels ofbis-Sulfonyl Azide (BSA) concentrate at 25% active BSA, Peroxide(Trigonox 101), or a combination of Peroxide (Trigonox 101) withtri-allyl cyanurate (TAC) as a co-agent. Below is a table describing the2.5 pound blends that were prepared.

A 0.877 g/ B cc, 1 0.877 g/cc, 5 C PER- MI, % MI, % ENGAGE ® BSA OXIDECoagent Blend (inventive) (inventive) 8100% ppm ppm ppm 1 100 0 0 2 100100 3 100 200 4 100 400 5 100 800 6 100 100 7 100 200 8 100 400 9 100800 10 100 800 800 11 70 30 0 0 12 70 30 800 13 70 30 800 14 70 30 800800 15 100 0 0 16 100 800 17 100 800 18 100 800 800

In the above table, samples A and B are ethylene/α-olefin multi-blockinterpolymers made in a manner similar to that described in Tables 2 and8 above. Sample A had a density of 0.877 g/cc with a 1 MI and sample Bhad a density of 0.877 g/cc with a 5 MI. Sample C is a commerciallyavailable comparative example called ENGAGE®8100 from The Dow ChemicalCompany having a density of 0.870 g/cc and a 1 MI. The BSA in the tablerefers to active BSA which is at a level of 25% in the concentrate. Theperoxide is 90% active. The physical nature of the BSA molecular melt isa powder, the peroxide a liquid, and the co-agent a granular crystal. Inthe case of the BSA samples silicone oil (Dow Corning 200 FLUID, a 20CST polydimethylsiloxane) was used as a surfactant to uniformly coat thepellets with the BSA powder. This was accomplished by first dry blendingthe pellets in a plastic bag. Approximately 2 ml of silicone fluid wasthen added to the pellets and tumbled in the bag to disperse the oil onthe pellet surface. The coated pellets were then removed to a new cleanbag. The BSA molecular melt was then sprinkled onto the pellets andtumbled by hand in the sealed air filled bag to disperse the molecularmelt onto the pellet surface. The second plastic bag was used tominimize loss of molecular melt on the oil coated surface of the initialbag. With the peroxide containing blends the peroxide was added dropwiseonto the pellets in the bag. The bag of pellets was air filled andsealed, then hand tumbled to disperse the peroxide throughout the pelletmixture. If a co-agent was used, the pulverized TAC granules were addedafter the peroxide was dispersed, the bag was air filled, sealed, andtumbled to uniformly disperse the TAC.

The above prepared samples were fed to a pre-heated twin screw extruder.The extruder is an 18 mm co-rotating 30 L/D Leistritz controlled by aHaake computer system and incorporates a series of conveying elementsand kneading block areas for shear heating, mixing and reacting. Thepolymer flows from left to right and finally past the tips through a dieforming a strand passing through a series of two water baths, through anair knife, and finally pelletized by a strand chopper into pellets whichwere collected and saved.

The extruder consisted of six zones and a heated die. The first zone wascooled with a circulating water jacket to prevent premature melting ofthe pellet feed and subsequent bridging of the feed zone. The fiveremaining zones were electrically heated and air cooled controlled at120, 150, 190, 190, and 190° C. The die was heated to 190° C. Thepellets were fed to the extruder by a K-TRON twin auger pellet feeder ata rate of 2-3 pounds/hour. The feed hopper was sealed and supplied witha flow of nitrogen to minimize oxidation of the polymer in the extruder.The transition from pellet feeder to extruder feed port was sealed withaluminum foil to also minimize air intrusion. The drive unit of theextruder was turning at 150 rpm resulting in a screw speed of 188 rpm.This would allow an extruder residence time of approximately 1.25-1.75minutes.

The following table below displays the extrusion parameters of thevarious blends prepared. The collected pellets prepared from thisreactive extrusion modification were subsequently submitted foranalyses.

Die BLEND Feed rate #/hr Melt Temp ° C. Torque m-g Pressure PSI 1 3.0197 6000 830 2 3.0 197 5700 870 3 2.9 197 5600 900 4 2.8 196 5700 945 52.9 198 6000 915 6 2.15 195 4700 675 7 2.0 195 4700 750 8 2.2 195 5000720 9 2.2 195 5200 725 10 1.75 200 6500 1350 11 2.9 196 5200 740 12 2.9196 5100 815 13 2.4 194 5300 700 14 2.0 196 5500 1200 15 3.0 196 5800805 16 2.8 196 5500 875 17 2.2 195 5100 740 18 1.5 200 6900 1550

Characterization of the Resins and Blends

Density

Density of the samples was measured by use of solvent-displacementmethod (based on the Archimedes' principle) which gives the specificgravity of the sample. Prior to the measurement a known volume of thesample was compression molded at 190° C. and then immersed in2-propanol. The volume of the solvent displaced was observed and as aresult the specific gravity of the specimen was computed. This testcomplies with ASTM D792, Method B.

Melt Index

I₂, measured in grams per 10 minutes, is done in accordance with ASTM D1238, Condition 190° C./2.16 kg. I₁₀ is measured in accordance with ASTMD 1238, Condition 190° C./10 kg.

Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry was performed on a TA InstrumentsQ1000 DSC equipped with an RCS cooling accessory and an auto sampler. Anitrogen purge gas flow of 50 ml/min was used. The sample was pressedinto a thin film and melted in the press at about 190° C. and thenair-cooled to room temperature (25° C.). About 3-10 mg of material wasthen cut, accurately weighed, and placed in a light aluminum pan (ca 50mg) which was later crimped shut. The thermal behavior of the sample wasinvestigated with the following temperature profile: the sample wasrapidly heated to 230° C. and held isothermal for 3 minutes in order toremove any previous thermal history. For the butene-based polymers, thesample was then cooled to −90° C. at 10° C./min cooling rate and held at−90° C. for 3 minutes. The sample was then heated to 230° C. at 10°C./min heating rate. For the octene-based polymers, the sample was thencooled to −40° C. at 10° C./min cooling rate and held at −40° C. for 3minutes. The sample was then heated to 190° C. at 10° C./min heatingrate. The first cooling and second heating curves were recorded.

Melt Rheology

All the dynamic mechanical measurements (viscosity vs. frequency andtemperature, loss and storage modulus vs. temperature) were measured onTA instruments ARES. The viscosity vs. frequency measurements wereperformed using a parallel plate configuration from 0.1-100 rad/s at 190C.

Thermal Mechanical Analysis (TMA)

Thermal Mechanical Analysis (TMA), that measures penetration of probe(ca. 1.1 mm in diameter) into a small cylindrical sample as temperatureis raised from ambient conditions, was performed. The samples werecompression molded into a cylindrical geometry of ca. 3.3 mm thick and 8mm in diameter. The temperature was raised from 25° C. to 190° C. at arate of 5° C./min with the probe applying a constant force of 1000 mN onthe surface of the sample.

Compression Set

Compression set was measured according to ASTM D 395 at ambient and 70°C. The sample was prepared by stacking 25.4 mm diameter round discs of3.2 mm, 2.0 mm, and 0.25 mm thickness until a total thickness of 12.7 mmis reached. The discs were cut from 12.7 cm×12.7 cm compression moldedplaques that were molded in a hot press under the following conditions:zero pressure for 3 min at 190° C., followed by 86 MPa for 2 min at 190°C., followed by cooling inside the press with cold running water runninginside the metal plates at 86 MPa.

Melt Strength

Melt strength of the base polymers and blends was measured at 190° C. ona Gottfert Rheotester 2000 and Gottfert Rheotens 71.97. The barrellength of the rheometer was 285 mm and width ca. 12 mm. A 30/2 die forthe extrusion of the polyethylene along with 1000 bar transducer wasutilized. When running melt strength, only the transducer was used toprevent the rheotester from getting overloaded and thereby preventingany damage to the rheometer. The sample was allowed to melt in thebarrel for ten minutes, followed by extrusion through the die at a rateof 0.27 mm/s (shear rate of ca. 38 s⁻¹). As the sample extrudes out ofthe die, it passes through the wheels of the Rheotens, which pulls thepolymer in a downward motion. As the wheel velocity increases, the forcerequired to pull the molten extrudate was measured in cN.

Tensile Properties and Shore A Hardness

Unoriented quenched compression molded films of ca. 0.4 mm thickness andplaques of thickness of 2 mm were produced on a hot press (Carver Model#4095-4PR1001R). Preweighed amounts of the pellets were placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film and plaques was then cooled in a separate set of metal platesin the press that were maintained at room temperature (ca. 21° C.).Stress-strain behavior in uniaxial tension was measured using ASTM D1708 on the films. Samples were stretched in an Instron™ at 300% min⁻¹at 21° C. Tensile strength, elongation at break and secant modulus at100% strain were reported from an average of 5 specimens. The plaqueswere utilized for the shore A hardness measurement on a Hardness Tester28217-A, Shore Instrument & Manufacturing Company, according toASTM-D676.

Data Table A, B, C, 0.877 g/cc, 1 0.877 g/cc, Engage Active Peroxide:Coagent, 70 C. MI 5 MI 8100, 0870 g/cc, BSA*, Trigonx TAC, C-set, blend#(inventive) (inventive) 1 MI ppm 101, ppm ppm % I2 I10 I10/I2 Mw 1 100 00 41 1.05 7.4 7.0 125000 2 100 100 44 0.92 6.7 7.2 128600 3 100 200 420.79 6.0 7.7 133700 4 100 400 36 0.59 5.1 8.7 139400 5 100 800 33 0.283.1 11.1 162900 6 100 100 42 0.93 7.0 7.5 124600 7 100 200 46 0.80 6.78.3 123700 8 100 400 47 0.56 5.7 10.2 127100 9 100 800 50 0.29 4.0 13.9138900 10 100 800 800 45 not — 227800 measurable 11 70 30 0 0 45 1.5310.5 6.8 111100 12 70 30 800 45 0.47 5.7 12.1 144500 13 70 30 800 500.51 6.4 12.6 125300 14 70 30 800 800 44 0.04 1.1 25.2 191800 15 100 0 0NM 1.0 8.08 8.5 110000 16 100 800 NM 0.33 4.1 12.4 139000 17 100 800 NM0.15 2.8 19.0 146000 18 100 800 800 NM not — 214400 measurable 15% LDPE662i w/ 1 MI, 0.877 g/cc Sample A 45 0.90 NM NM NM 30% LDPE 662i w/ 1 MI0.877 g/cc Sample A 48 0.70 NM NM NM ENX896800 Control NM NM NMENX892100 Control NM NM NM A, B, C, 0.877 g/cc, 1 0.877 g/cc, EngageActive Rheology MI 5 MI 8100, 0870 g/cc, BSA*, melt drawability, ratio,blend# (inventive) (inventive) 1 MI ppm Mn Mw/Mn str., cN mm/sh_(0.1)/h₁₀₀ Shore A 1 100 0 61000 2.0 3.1 217.0 4 2 100 100 63000 2.03.2 138.0 5 3 100 200 63600 2.1 4.7 130.0 6 4 100 400 65200 2.1 6.6132.0 8 5 100 800 65100 2.5 9.8 60.0 23 6 100 61300 2.0 3.5 170.0 5 7100 56300 2.2 4.6 155 7 8 100 56000 2.3 6.3 150.0 11 9 100 60000 2.3 7.9125 23 10 100 61500 3.7 40 34 54 11 70 30 0 54100 2.1 2 280 3 12 70 30800 58600 2.5 7.6 84 17 13 70 30 49800 2.5 7.1 148 17 14 70 30 47500 4.034 35 43 15 100 0 55500 2.0 3.7 159 5 16 100 800 59400 2.3 9.5 100 19 17100 57300 2.5 10 121 36 18 100 55700 3.8 44 34 3740 15% LDPE 662i w/ 1MI, 0.877 g/cc Sample A NM NM 14 227 6 85 30% LDPE 662i w/ 1 MI 0.877g/cc Sample A NM NM 29 106 9 88 ENX896800 Control NM NM 7.4 88 95ENX892100 Control NM NM 4.6 107 34 *use silicon oil to disperse the BSAmolecular melt 2 lb each RMS, Melt Strength, Low Shear Viscosity (Creep)and Low Extensional Viscosity I2 and I10, GPC, Compression set onselected samples AO analysis on selected sample

FIG. 16 shows the melt strength modification of polymer ‘A’ withperoxide. It can be seen that the melt strength increases withincreasing amount of peroxide in comparison to the melt strength of theuntreated polymer ‘A’, e.g., the melt strength at 800 ppm of peroxidewas ca. 2 times that of the untreated polymer ‘A’. Furthermore, whenco-agent was added with the peroxide the melt strength enhancement wasca. 12-15 times that of the untreated polymer ‘A’.

FIG. 17 shows the melt strength modification of polymer ‘A’ with BSA. Itcan be seen that the melt strength increases with increasing amount ofBSA in comparison to the melt strength of the untreated polymer ‘A’,e.g., the melt strength at 800 ppm of BSA was ca. 3 times that of theuntreated polymer ‘A’. Recall that at this same level of modification,the peroxide treatment resulted in only ca. 2 times enhancement of themelt strength of the untreated polymer ‘A’, thereby indicating that BSAwas more effective in melt strength enhancement than peroxide at thislevel of modification.

FIG. 18 shows the melt shear rheology (viscosity versus frequency)modification of polymer ‘A’ with peroxide. With increasing amounts ofperoxide, the zero shear viscosity and shear thinning increase. Therheology ratio, which is the ratio of viscosity at 0.1 rad/s to that at100 rad/s, gives an estimate of shear thinning. This data is listed inthe Table provided earlier where all the general properties are listed.With the addition of peroxide, the rheology ratio increases from 4 (forthe untreated polymer ‘A’) to 23 at 800 ppm of peroxide modification.Interestingly, when 800 ppm of co-agent was added with the 800 ppm ofperoxide, the rheology ratio was as high as 54. A higher rheology ratioor higher shear thinning implies higher throughput at higher shearrates.

FIG. 19 shows the melt shear rheology (viscosity versus frequency)modification of polymer ‘A’ with BSA. With increasing amounts of BSA,the zero shear viscosity and shear thinning increase. With the additionof BSA, the rheology ratio increases from 4 (for the untreated polymer‘A’) to 23 at 800 ppm of BSA modification.

FIG. 20 shows the 70° C. compression set for the peroxide and BSAmodified polymer ‘A’ as function of the ppm of the modifier. Thecompression set of the untreated polymer ‘A’ (also listed in the Tablewhere all the general properties are listed) is ca. 41%. Modificationwith peroxide leads to a steady, but not significant, increase in thecompression set, e.g., the compression set at 800 ppm of peroxide is ca.50%. Interestingly, modification with BSA leads to lower compressionset, especially at higher amounts of BSA in the formulation, e.g., at400 and 800 ppm, the compression set was 36 and 33% respectively.Furthermore, it can be said that the modification with BSA is moreeffective in reducing the compression set of the untreated polymer ‘A’than that by peroxide, especially at amounts equivalent or larger than400 ppm in the formulation.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

1. A composition comprising: at least one silane-graftedethylene/α-olefin multi-block polymer, wherein the silane-graftedethylene/α-olefin multi-block polymer is formed from an olefininterpolymer having a melt viscosity less than 50,000 cP at 177° C. 2.The composition of claim 1 wherein the silane-grafted ethylene/α-olefinmulti-block polymer is formed from an olefin interpolymer having atleast one melting point, T_(m), in degrees Celsius, and a density, d*,in grams/cubic centimeter, and wherein the numerical values of thevariables correspond to the relationship:T _(m)>−2002.9+4538.5(d*)−2422.2(d*)²,and wherein the olefininterpolymer has a M_(w)/M_(n) from 1.7 to 3.5.
 3. The composition ofclaim 1, wherein the at least one silane-grafted ethylene/α-olefinmulti-block polymer is formed from an olefin interpolymer having anumber average molecular weight from 5,000 to 25,000.
 4. The compositionof claim 1, wherein the silane-grafted ethylene/α-olefin multi-blockpolymer has a density from 0.855 g/cc to 0.955 g/cc.
 5. The compositionof claim 1, wherein the at least one silane-grafted ethylene/α-olefinmulti-block polymer is formed from an olefin multi-block interpolymerhaving a density from about 0.855 g/cc to about 0.93 g/cc.
 6. Thecomposition of claim 1 comprising greater than, or equal to, 0.05 wt %of a silane-grafted moiety based on the total weight of silane-graftedethylene/α-olefin multi-block polymer.
 7. The composition of claim 1,wherein the silane-grafted ethylene/α-olefin multi-block polymer isformed from a silane compound selected from the group consisting ofvinyltrialkoxysilane, vinyltriacyloxysilane, and vinyltrichlorosilane.8. The composition of claim 1, wherein the silane-graftedethylene/α-olefin multi-block polymer is crosslinked.
 9. The compositionof claim 1, having a Peel Adhesion Failure Temperature (PAFT) of greaterthan, or equal to, 43° C.
 10. The composition of claim 1 having a ShearAdhesion Failure Temperature (SAFT) of greater than, or equal to 60° C.11. The composition of claim 1 comprising a second polymer.
 12. Acomposition comprising: at least one silane-grafted ethylene/α-olefinmulti-block polymer, wherein the silane-grafted ethylene/α-olefinmulti-block polymer is formed from an olefin interpolymer having a meltviscosity less than 50,000 cP at 177° C.; tackifier; and an oil.
 13. Thecomposition of claim 12 wherein the silane-grafted ethylene/α-olefinmulti-block polymer is formed from an olefin interpolymer having atleast one melting point, T_(m), in degrees Celsius, and a density, d*,in grams/cubic centimeter, and wherein the numerical values of thevariables correspond to the relationship:T _(m)>−2002.9+4538.5(d*)−2422.2(d*)²,and wherein the olefininterpolymer has a M_(w)/M_(n) from 1.7 to 3.5.
 14. The composition ofclaim 12 comprising a second polymer.
 15. The composition of claim 14wherein the second polymer is selected from the group consisting ofpolypropylene, polyethylene, ethylene-vinyl acetate, ethylene/vinylalcohol copolymer, polystyrene, impact modified polystyrene,acrylonitrile-butadiene-styrene, styrene/butadiene block copolymer andhydrogenated derivatives thereof, thermoplastic polyurethane, polyamide,polyester, polycarbonate, engineering thermoplastic, polyvinyl alcohol,polyvinylidene chloride, polyvinyl chloride, cellulose fiber, and woolfibers.
 16. The composition of claim 12 wherein the silane-graftedethylene/α-olefin multi-block polymer is cross-linked.
 17. A compositioncomprising: crosslinked silane-grafted ethylene/α-olefin multi-blockinterpolymer, wherein the silane-grafted ethylene/α-olefin multi-blockinterpolymer prior to crosslinking has a M_(w)/M_(n) from 1.7 to 3.5, atleast one melting point, T_(m), in degrees Celsius, and a density d*, ingrams/cubic centimeter, and wherein the numerical values of thevariables correspond to the relationship:T _(m)>−2002.9+4538.5(d*)−2422.2(d*)².
 18. The composition of claim 17wherein the silane-grafted ethylene/α-olefin multi-block polymer isformed from an olefin interpolymer having a melt viscosity less than50,000 cP at 177° C.
 19. The composition of claim 17 comprising atackifier and an oil.
 20. The composition of claim 17 comprising asecond polymer.